JP5418006B2 - Biodegradable laminated sheet and processed product - Google Patents

Description

  The present invention relates to a biodegradable laminated sheet obtained by laminating an aliphatic polyester resin composition having good moldability and good secondary processability and having a suppressed odor on a base material, and the biodegradable laminated sheet Relates to processed products using

  In modern society, paper, plastics, aluminum foil, etc. are used in a wide range of applications such as packaging materials such as various foods, medicines, miscellaneous materials, powders, solids, etc., agricultural materials, and building materials. . In particular, plastics are excellent in strength, water resistance, moldability, transparency, production cost, and the like, and are used in many applications as bags, containers and the like.

  Currently, plastics used for these applications include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, and the like. However, the above plastics do not biodegrade or hydrolyze in the natural environment, or the degradation rate is extremely slow, so that the buried plastic remains in the soil or the discarded plastic damages the landscape. Sometimes. In addition, when plastic is incinerated, it generates harmful gases and damages the incinerator.

  As a means for solving these problems, many studies have been made on materials having biodegradability. Representative examples of the biodegradable material include aliphatic polyester resins such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate. In order to shape these aliphatic polyester resins into the shape of sheets, films, containers, trays, bottles, etc., various molding methods such as extrusion molding, blow molding, paper laminating, vacuum molding, vacuum pressure forming, etc. are used. I can do it. However, since the above-mentioned aliphatic polyester resin usually has a low melt tension, the drawdown during vacuum sheet molding is large, the sticking to the cooling roll during lamination sheet molding is large, the neck-in is large, etc. Often the properties are insufficient.

  Therefore, in order to improve the moldability of the biodegradable material, for example, in Patent Document 1, melt tension is obtained by melt-kneading polylactic acid, aliphatic polyester resin, and organic peroxide to finely crosslink the resin. An aliphatic polyester resin composition with improved moldability and improved moldability is disclosed.

Patent Document 2 discloses an aliphatic polyester resin composition in which crosslinking is uniformly introduced by mixing an aliphatic polyester resin, an organic peroxide, and a chain transfer agent and melt-kneading them.
Patent Document 3 discloses a method of obtaining a laminate by controlling the resin pressure during processing without using a coupling agent in the laminate of an aliphatic polyester resin.

JP 2001-26658 A JP 2001-26696 A JP 2006-272712 A

  As a result of intensive studies to solve the above problems, the present inventors have melt-kneaded an aliphatic polyester resin having a copolymer component having a double bond within a certain range and an organic peroxide. Because the double bond and organic peroxide react efficiently, cross-linking develops efficiently with a small amount of organic peroxide, resulting in excellent melt tension. The present invention was completed by finding that a biodegradable laminated sheet having a property and an organic peroxide-derived odor and a paper container processed from the biodegradable laminated sheet can be provided.

That is, the gist of the present invention is a method for producing a biodegradable laminated sheet obtained by laminating a resin composition obtained by mixing an aliphatic polyester resin and an organic peroxide on a substrate,
The aliphatic polyester resin comprises an aliphatic dicarboxylic acid unit represented by the following formula (1), an aliphatic diol unit represented by the following formula (2), and an aliphatic hydroxy represented by the following formula (3). One or more aliphatic hydroxycarboxylic acid units selected from the group consisting of carboxylic acid units and aliphatic hydroxycarboxylic acid units represented by the following formula (4), and aliphatic unsaturation represented by the following formula (5) One or more aliphatic units selected from the group consisting of a dicarboxylic acid unit, an aliphatic unsaturated dicarboxylic acid unit represented by the following formula (6), and an aliphatic unsaturated dicarboxylic acid unit represented by the following formula (7): at least look at containing the saturated dicarboxylic acid units,
The total amount of the units represented by the formula (3), the formula (4), the formula (5), the formula (6) and the formula (7) is the total amount of all units contained in the aliphatic polyester resin. The total of the units represented by the formula (3) and the formula (4) is 0.0010 mol% or more and 0.50 mol% or less with respect to the total amount of 100 mol%. (6) and molar ratio to the total of the unit represented by the formula (7) state, and are 1.0 to 7.0, with respect to 100 parts by weight of the aliphatic polyester resin,
The organic peroxide is mixed in a ratio of 0.0001 parts by weight or more and 0.06 parts by weight or less, and the present invention resides in a method for producing a biodegradable laminated sheet (Claim 1).

（式中、Ｒ¹は、炭素数が０〜４０の脂肪族飽和炭化水素基を表す。）

(In the formula, R ¹ represents an aliphatic saturated hydrocarbon group having 0 to 40 carbon atoms.)

（式中、Ｒ²は、炭素数が２〜１０の脂肪族炭化水素基を表す。）

(In the formula, R ² represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms.)

（式中、Ｒ³は、炭素数１〜２０の脂肪族炭化水素基を表す。）

(In the formula, R ³ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)

（式中、Ｒ⁴は、炭素数１〜２０の脂肪族炭化水素基を表す。）

(In the formula, R ⁴ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)

（式中、Ｒ⁵は、一つ以上の二重結合を有する炭素数２〜２０の脂肪族炭化水素基を表す。）

(In the formula, R ⁵ represents a C 2-20 aliphatic hydrocarbon group having one or more double bonds.)

（式（６）及び式（７）は、ともに二重結合に関する幾何異性体であって、式（６）はトランス型、式（７）はシス型を表す。ｒ及びｓは、それぞれ独立に、０〜１７の整数を表す。Ｒ⁸は、水素又は炭素数が１〜１７の脂肪族炭化水素基を表す。）

(Formula (6) and Formula (7) are both geometrical isomers relating to a double bond, wherein Formula (6) represents a trans form, and Formula (7) represents a cis form. And represents an integer of 0 to 17. R ⁸ represents hydrogen or an aliphatic hydrocarbon group having 1 to 17 carbon atoms.

  Furthermore, it is preferable that the amount of vinyl groups present at the terminal of the aliphatic polyester resin is 0.002 mol% or more with respect to the aliphatic polyester resin.

The unit represented by the formula (5) is an aliphatic unsaturated dicarboxylic acid unit represented by the following formula (8) and / or the following formula (9), and is included in the aliphatic polyester resin. It is preferable that the molar ratio of the unit represented by Formula (8) is 8.5 or less with respect to the unit represented by Formula (9).

（式（８）及び式（９）は、ともに二重結合に関する幾何異性体であって、式（８）はトランス型、式（９）はシス型を表す。ｍ及びｎは、それぞれ独立に、０〜１８の整数を表す。Ｒ⁶及びＲ⁷は、それぞれ独立に、水素又は炭素数が１〜１８の脂肪族炭化水素基を表す。）

(Formula (8) and Formula (9) are both geometrical isomers relating to a double bond, wherein Formula (8) represents a trans form, and Formula (9) represents a cis form. And represents an integer of 0 to 18. R ⁶ and R ⁷ each independently represents hydrogen or an aliphatic hydrocarbon group having 1 to 18 carbon atoms.

  Furthermore, it is preferable that the unit represented by the formula (3) is a unit derived from malic acid.

  At this time, the unit represented by the formula (4) is preferably a unit derived from citric acid.

  The organic peroxide is at least one compound selected from the group consisting of ketone peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, and hydroperoxide. It is preferable.

  When the reduced viscosity at 30 ° C. of the aliphatic polyester resin is η and the reduced viscosity at 30 ° C. of the aliphatic polyester resin composition is η ′, a value obtained by dividing η ′ by η is 1.05 or more. It is preferable that it is 1.80 or less.

  And when the melt tension at 190 ° C. of the aliphatic polyester resin is F and the melt tension at 190 ° C. of the aliphatic polyester resin composition is F ′, the value obtained by dividing F ′ by F is 1.5 or more. It is preferable that

Then, 190 ° C. of the aliphatic polyester resin for melt viscosity at a shear rate of 1000 s ^-1, a ratio of the melt viscosity at 190 ° C. shear rate 10s ^-1 [rho, also, 190 ° C. of the aliphatic polyester resin composition for melt viscosity at a shear rate of 1000 s ^-1, a ratio of the melt viscosity at 190 ° C. shear rate 10s ^-1 it is taken as p ', a value obtained by dividing the p' in ρ is 1.1 to 3.0 It is preferable that

  And it is preferable that content of a gel part is less than 10 weight%.

  Moreover, it exists in the paper bag which processed the biodegradable laminated sheet as described in any one of Claims 1-5, a paper container, and a paper box.

  According to the present invention, the biodegradability is excellent in melt tension, has good moldability with less neck-in and enhanced adhesive force, is excellent in punchability as secondary workability, and has further suppressed odor. A laminated sheet, a biodegradable laminated sheet and a processed product obtained by processing the laminated sheet, preferably a paper container can be provided.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the examples and embodiments described below, and can be arbitrarily modified and implemented without departing from the gist of the present invention. I can do it.

  In the present invention, a resin composition containing a specific resin as a component may be called with the name of the resin as the main component. Here, the “main component” refers to a component that occupies 50% by weight or more of the composition. That is, the “aliphatic polyester resin composition” refers to a resin composition containing an aliphatic polyester resin as a main component.

  Further, in this specification, the term “polymer” refers to a polymer composed of a single type of repeating structural unit (so-called “homopolymer”) and a polymer composed of a plurality of types of repeating structural units (so-called “polymer”). It is used as a concept including “copolymer”).

  In the following description, a partial structural unit of a polymer derived from a certain monomer is represented by adding the word “unit” to the name of the monomer. For example, the partial structural unit derived from dicarboxylic acid is represented by the name “dicarboxylic acid unit”.

Moreover, the monomer which gives the same partial structural unit is named generically by the name which replaced the "unit" of the name of the partial structural unit with "component." For example, monomers such as aromatic dicarboxylic acids and aromatic dicarboxylic acid diesters form aromatic dicarboxylic acid units, even if the reaction in the process of forming the polymer is different. Therefore, these aromatic dicarboxylic acids and aromatic dicarboxylic acid diesters are collectively referred to as “aromatic dicarboxylic acid component”.
The biodegradable laminate sheet in the present invention is a generic term for a laminate as long as the resin composition described in the present invention is laminated on a base material, and the film is also a biodegradable laminate sheet of the present invention. There is no particular limitation on the thickness and the like contained in Preferably, there is no particular problem as long as it has a thickness that can be processed into a paper bag, a paper container, a paper box, an agricultural multi-film or the like that is a secondary processed product. Specifically, the lower limit of the resin layer is 10 μm or more, preferably 12 μm or more, and more preferably 20 μm or more. Furthermore, the upper limit is 100 μm or less, preferably 80 μm, and more preferably 50 μm or less. Below the lower limit, the physical properties of the laminated sheet may be deteriorated, and the heat sealability is also deteriorated. On the other hand, when the upper limit is exceeded, deterioration of punchability, which is secondary workability, and sticking to a cooling roll, etc., are problematic.

[1. Aliphatic polyester resin composition of the present invention]
The aliphatic polyester resin composition of the present invention (hereinafter referred to as “the resin composition (A ′) of the present invention” as appropriate) is the aliphatic polyester resin described below (hereinafter referred to as “the aliphatic polyester of the present invention as appropriate”). Resin (A) "and an organic peroxide (hereinafter referred to as" organic peroxide (B) "as appropriate) are mixed. That is, the resin composition (A ') Is an aliphatic dicarboxylic acid unit represented by the following formula (1), an aliphatic diol unit represented by the following formula (2), and an aliphatic hydroxycarboxylic acid unit represented by the following formula (3). And one or more aliphatic hydroxycarboxylic acid units selected from the group consisting of aliphatic hydroxycarboxylic acid units represented by the following formula (4), and aliphatic unsaturated dicarboxylic acid units represented by the following formula (5): An aliphatic unsaturated dicarbohydrate represented by the following formula (6) An aliphatic polyester resin (A) comprising at least one acid unit and at least one aliphatic unsaturated dicarboxylic acid unit selected from the group consisting of aliphatic unsaturated dicarboxylic acid units represented by the following formula (7): The total amount of units represented by the formula (3), the formula (4), the formula (5), the formula (6) and the formula (7) is included in the aliphatic polyester resin (A). The total amount of all the units is 0.0010 mol% to 0.50 mol%, and the total of the units represented by the above formula (3) and the above formula (4) is the above formula. (5) The aliphatic polyester resin (A) and the organic peroxide that are 1.0 or more and 7.0 or less as a molar ratio with respect to the total of the units represented by the formula (6) and the formula (7). In the aliphatic polyester resin composition (A ′) containing (B), The organic peroxide (B) is mixed at a ratio of 0.0001 part by weight or more and 0.06 part by weight or less with respect to 100 parts by weight of the aliphatic polyester resin (A). By melt-kneading, the aliphatic polyester resin (A) of the present invention is crosslinked with the organic peroxide (B) to constitute the resin composition (A ′) of the present invention. A ′) may contain one kind of the aliphatic polyester resin (A) of the present invention alone or two or more kinds of the aliphatic polyester resin (A) of the present invention in any ratio and combination.

（式中、Ｒ¹は、炭素数が０〜４０の脂肪族飽和炭化水素基を表す。）

(In the formula, R ¹ represents an aliphatic saturated hydrocarbon group having 0 to 40 carbon atoms.)

（式中、Ｒ²は、炭素数が２〜１０の脂肪族炭化水素基を表す。）

(In the formula, R ² represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms.)

（式中、Ｒ³は、炭素数１〜２０の脂肪族炭化水素基を表す。）

(In the formula, R ³ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)

（式中、Ｒ⁴は、炭素数１〜２０の脂肪族炭化水素基を表す。）

(In the formula, R ⁴ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)

（式中、Ｒ⁵は、一つ以上の二重結合を有する炭素数２〜２０の脂肪族炭化水素基を表す。）

(In the formula, R ⁵ represents a C 2-20 aliphatic hydrocarbon group having one or more double bonds.)

（式（６）及び式（７）は、ともに二重結合に関する幾何異性体であって、式（６）はトランス型、式（７）はシス型を表す。ｒ及びｓは、それぞれ独立に、０〜１７の整数を表す。Ｒ⁸は、水素又は炭素数が１〜１７の脂肪族炭化水素基を表す。）

(Formula (6) and Formula (7) are both geometrical isomers relating to a double bond, wherein Formula (6) represents a trans form, and Formula (7) represents a cis form. And represents an integer of 0 to 17. R ⁸ represents hydrogen or an aliphatic hydrocarbon group having 1 to 17 carbon atoms.

[1-1. composition]
[1-1-1. Aliphatic polyester resin (A)]
(Structural unit)
(Aliphatic dicarboxylic acid unit represented by Formula (1))
In the present invention, R ¹ of the aliphatic dicarboxylic acid unit represented by the above formula (1) (hereinafter appropriately referred to as “aliphatic dicarboxylic acid unit (1)”) usually has 0 or more carbon atoms, preferably Is 2
In addition, the aliphatic hydrocarbon group is usually 40 or less, preferably 20 or less, more preferably 10 or less, and particularly preferably 4 or less. Note that an aliphatic hydrocarbon group having 0 carbon atoms is R ^1.
Indicates that does not exist. R ¹ may be a chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, which is a combination of a chain aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group. May be. In the case of a chain aliphatic hydrocarbon group, it may be a linear aliphatic hydrocarbon group or a branched chain aliphatic hydrocarbon group. In the case of a cycloaliphatic hydrocarbon group, it may be a single ring, or may be one in which a plurality of rings are bonded to each other or condensed. Moreover, the aliphatic polyester resin (A) of this invention may contain individually 1 type of the aliphatic dicarboxylic acid unit (1), and may contain 2 or more types by arbitrary ratios and combinations.

The aliphatic dicarboxylic acid unit (1) is optional as long as it is a unit derived from an aliphatic dicarboxylic acid containing R ¹ having a carbon number in the range described above and / or a derivative thereof.

The aliphatic dicarboxylic acid unit (1) used in the present invention is derived from an aliphatic dicarboxylic acid and / or a derivative thereof (hereinafter collectively referred to as “aliphatic dicarboxylic acid component (1)”). To do. As long as the aliphatic dicarboxylic acid component (1) is an aliphatic compound and an alicyclic compound having two carboxyl groups, it is optional as long as the effects of the present invention are not significantly impaired. Specific examples of the aliphatic carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanoic acid, dimer acid, and cyclohexanedicarboxylic acid. Specific examples of the aliphatic dicarboxylic acid derivatives include the above-mentioned aliphatic dicarboxylic acid methyl esters, ethyl esters, propyl esters, butyl esters and other lower alkyl esters, and succinic anhydrides and other aliphatic dicarboxylic acid cyclic acids. An anhydride etc. are also mentioned. Among these, as the aliphatic dicarboxylic acid, adipic acid, succinic acid, dimer acid, or a mixture thereof is preferable, and a mixture containing succinic acid as a main component is more preferable. Further, as the derivative of the aliphatic dicarboxylic acid, methyl ester of adipic acid, methyl ester of succinic acid, or a mixture thereof is preferable. As the aliphatic dicarboxylic acid component (1), one type may be used alone, or two or more types may be used in optional ratio and combination.

  The “main component” in the present invention is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more with respect to all dicarboxylic acid units contained in the aliphatic polyester resin (A). Particularly preferably, it indicates a component formed from units contained in an amount of 90 mol% or more.

The amount of the aliphatic dicarboxylic acid unit (1) contained in the aliphatic polyester resin (A) can be quantified using a known analysis method such as ¹ H-NMR, for example. Specifically, for example, a solution prepared by dissolving 20mg of the aliphatic polyester resin (A) in deuterochloroform 0.6ml a measurement sample, using a Bruker BioSpin Co. Avance 400 spectrometer at room temperature for ¹ It can be quantified by measuring the H-NMR spectrum. The measurement conditions at this time are not particularly limited as long as they can be suitably quantified, but are described in the section of [NMR measurement conditions].

  Further, in the aliphatic polyester resin (A) of the present invention, in addition to the unit derived from the aliphatic dicarboxylic acid component (1), aromatic dicarboxylic acid and / or Alternatively, units derived from derivatives thereof (hereinafter collectively referred to as “aromatic dicarboxylic acid component (1)” as appropriate) (hereinafter referred to as “aromatic dicarboxylic acid unit (1)” as appropriate). These may be included in any ratio and combination. As the aromatic dicarboxylic acid component (1), any aromatic compound having two carboxyl groups can be used as long as the effects of the present invention are not significantly impaired. As the aromatic dicarboxylic acid component (1), one type may be used alone, or two or more types may be used in optional ratio and combination.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and the like. Specific examples of the aromatic dicarboxylic acid derivative include lower alkyl esters such as methyl ester, ethyl ester, propyl ester, and butyl ester of the above aromatic dicarboxylic acid. Among these, terephthalic acid is preferable as the aromatic dicarboxylic acid, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid.

  When the aliphatic polyester resin (A) of the present invention contains the aromatic dicarboxylic acid unit (1), the amount of the aromatic dicarboxylic acid unit (1) contained in the aliphatic polyester resin (A) of the present invention It is usually 50 mol% or less, preferably 30 mol% or less, more preferably 10 mol% or less, based on the total dicarboxylic acid unit contained.

In addition, the aliphatic dicarboxylic acid unit (1) and / or the aromatic dicarboxylic acid unit (1) (hereinafter collectively referred to as “dicarboxylic acid unit (1)” as appropriate) are given from biomass resources. May be. Biomass resources include, for example, wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil scum, persimmon, buckwheat, soybean, fat, waste paper, papermaking residue , Marine product residue, livestock excrement, sewage sludge, food waste and the like. Among them, plant resources such as wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil residue, buckwheat, soy, oil, waste paper, paper residue Preferably, wood, rice straw, rice husk, old rice, corn, sugar cane, cassava, sago palm, straw, oil, fat, waste paper, and papermaking residue are more preferable, and corn, sugar cane, cassava, and sago palm are more preferable. These biomass resources usually contain elemental nitrogen; many alkali metals such as sodium and potassium; alkaline earth metals such as magnesium and calcium. One type of biomass resource may be used alone, or two or more types may be used in any ratio and combination.
Examples of carbon sources produced from the above biomass resources include hexoses such as glucose, mannose, galactose, fructose, sorbose, tagatose; pentoses such as arabinose, xylose, ribose, xylulose, ribulose; pentose, saccharose, starch, cellulose Disaccharides and polysaccharides such as butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, monoctinic acid, arachidic acid, eicosene Fats and oils such as acid, arachidonic acid, behenic acid, erucic acid, docosapentaenoic acid, docosahexaenoic acid, lignoceric acid, ceracolonic acid; polyalcohols such as glycerin, mannitol, xylitol, ribitol Sex carbohydrate; and the like. Among these, glucose, fructose, and xylose are preferable, and glucose is particularly preferable. As a carbon source derived from a broader plant resource, cellulose which is a main component of paper is preferable. A carbon source may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

Using these carbon sources, dicarboxylic acid component ( 1) is synthesized. Among these, what is synthesize | combined by the fermentation method by microbial conversion is preferable for the synthesis | combination of dicarboxylic acid component (1).
The aliphatic dicarboxylic acid component (1) is preferably less colored. The yellowness (YI value) of the aliphatic dicarboxylic acid component (1) is usually −20 or more, preferably −10 or more, more preferably −5 or more, further preferably −3 or more, particularly preferably −1 or more. The upper limit is usually 50 or less, preferably 20 or less, more preferably 10 or less, still more preferably 6 or less, and particularly preferably 4 or less. When the YI value is too small, a large amount of capital investment may be required for production of the aliphatic dicarboxylic acid component (1), or a great amount of production time may be required. Moreover, when YI value is too large, coloring of the aliphatic polyester resin (A) of this invention may become remarkable. The YI value can be measured by a method based on JIS K7105, for example.

(Aliphatic diol unit represented by Formula (2))
In the present invention, R ² of the aliphatic diol unit represented by the above formula (2) (hereinafter appropriately referred to as “aliphatic diol unit (2)”) usually has 2 or more carbon atoms, preferably 4 carbon atoms. In addition, the upper limit is usually an aliphatic hydrocarbon group of 10 or less, preferably 6 or less. R ² is
It may be a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or a combination of a chain aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group. In the case of a chain aliphatic hydrocarbon group, it may be a linear aliphatic hydrocarbon group or a branched chain aliphatic hydrocarbon group. In the case of a cycloaliphatic hydrocarbon group, it may be a single ring, or may be one in which a plurality of rings are bonded to each other or condensed. Moreover, the aliphatic polyester resin (A) of this invention may contain individually 1 type of the aliphatic diol unit (2), and may contain 2 or more types by arbitrary ratios and combinations.

The aliphatic diol unit (2) is optional as long as it is a unit derived from an aliphatic diol containing R ² having a carbon number in the above-described range and / or a derivative thereof.

  The aliphatic diol unit (2) used in the present invention is derived from an aliphatic diol and / or a derivative thereof (hereinafter collectively referred to as “aliphatic diol component (2)”). is there. As long as the aliphatic diol component (2) is an aliphatic and alicyclic compound having two hydroxyl groups, it is optional as long as the effects of the present invention are not significantly impaired. Specific examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, 1,4-cyclohexanedi Methanol etc. are mentioned. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferable, and ethylene glycol and 1,4-butanediol are more preferable. 1,4-butanediol is particularly preferred. As the aliphatic diol component (2), one kind may be used alone, and two kinds or more may be used in optional ratio and combination.

In addition, the quantity of the aliphatic diol unit (2) contained in an aliphatic polyester resin (A) can be measured similarly to the case of said aliphatic dicarboxylic acid unit (1), for example. In this case, the sample preparation conditions and ¹ H-NMR measurement conditions were aliphatic diol units (2
) Is not particularly limited as long as it can be suitably quantified. For example, the aliphatic diol unit (2) can be quantified by following the condition in which the amount of the aliphatic dicarboxylic acid unit (1) is quantified.

  In addition, in the aliphatic polyester resin (A) of the present invention, in addition to the unit derived from the aliphatic diol component (2), aromatic diol and / or derivatives thereof (hereinafter collectively referred to as Units derived from “aromatic diol component (2)” as appropriate (hereinafter referred to as “aromatic diol units (2)” as appropriate) may be included in any ratio and combination. As the aromatic diol component (2), any aromatic compound having two hydroxyl groups can be used as long as the effects of the present invention are not significantly impaired. However, the aromatic diol preferably has 6 or more carbon atoms and the upper limit is preferably 15 or less. As the aromatic diol component (2), one kind may be used alone, and two kinds or more may be used in optional ratio and combination.

  Specific examples of the aromatic diol component (2) include hydroquinone, 1,5-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bis (p-hydroxyphenyl) methane and bis (p-hydroxyphenyl) -2,2 -Propane and the like.

  When the aliphatic polyester resin (A) of the present invention contains the aromatic diol unit (2), the amount of the aromatic diol unit (2) contained is the total amount contained in the aliphatic polyester resin (A) of the present invention. It is usually 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, based on the diol unit.

  Moreover, as an aliphatic diol component (2), both terminal hydroxy polyether may be sufficient. As both-terminal hydroxy polyether, the number of carbon atoms is usually 4 or more, preferably 10 or more, and usually 1000 or less, preferably 200 or less, more preferably 100 or less.

Specific examples of both terminal hydroxy polyethers include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly 1,3-propanediol, poly 1,6-hexamethylene glycol, and the like. In addition, a copolymerized polyether of polyethylene glycol and polypropylene glycol can be used. Both terminal hydroxy polyether and copolymer polyether may be used alone, or two or more may be used in any ratio and combination.

  At this time, the use amount of both terminal hydroxy polyethers is usually 90% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less based on the weight of the aliphatic polyester resin (A). Is desirable.

  The aliphatic diol unit (2) and / or the aromatic diol unit (2) (hereinafter collectively referred to as “diol unit (2)” as appropriate) are derived from biomass resources. May be. Specifically, for example, the diol component (2) may be produced directly from a carbon source such as glucose by a fermentation method, or a dicarboxylic acid, a dicarboxylic acid anhydride, or a cyclic ether obtained by the fermentation method is chemically reacted. You may convert into a diol compound.

  More specifically, for example, 1,4-butanediol is produced by chemical synthesis from succinic acid, succinic anhydride, succinic ester, maleic acid, maleic anhydride, maleic ester, tetrahydrofuran, γ-butyrolactone, etc. Alternatively, 1,4-butanediol may be produced from 1,3-butadiene obtained by a fermentation method.

  Furthermore, a method of producing the diol component (2) from biomass resources by a known organic chemical catalytic reaction is also actively used. For example, when pentose is used as a carbon source obtained from biomass resources, the diol component (2) such as butanediol can be easily produced by a known dehydration reaction, catalytic reaction or the like.

  The diol component (2) is usually used as a raw material for the aliphatic polyester resin (A) after impurities such as oxidation products are removed by a purification step such as distillation. However, the diol component (2) may contain a small amount of an oxidation product of the diol component (2). Specifically, the amount of the oxidation product is usually 1 ppm or more with respect to the total amount of the diol component (2), preferably 10 ppm or more, more preferably 100 ppm or more from the viewpoint of economy of the purification process, The upper limit is usually 10,000 ppm or less, preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less.

  As specific examples of the oxidation product of the diol component (2), in addition to the oxide of the diol component (2), a hydrogen atom of a hydroxyl group such as 2- (4-hydroxybutyloxy) tetrahydrofuran is substituted with tetrahydrofuran. Compounds and the like. The oxidation product of the diol component (2) may be included singly or in combination of two or more in any ratio and combination.

(Aliphatic hydroxycarboxylic acid unit represented by Formula (3))
In the present invention, R ³ of the aliphatic hydroxycarboxylic acid unit represented by the above formula (3) (hereinafter referred to as “aliphatic hydroxycarboxylic acid unit (3)” as appropriate) usually has 1 or more carbon atoms. From the viewpoint of high heat resistance of the resin, it is preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 8 or less, and further preferably 3 or less aliphatic hydrocarbon group from the viewpoint of easy availability. Represent. R ³ may be a chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, which is a combination of a chain aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group. May be. In the case of a chain aliphatic hydrocarbon group, it may be a linear aliphatic hydrocarbon group or a branched chain aliphatic hydrocarbon group. In the case of a cycloaliphatic hydrocarbon group, it may be a single ring, or may be one in which a plurality of rings are bonded to each other or condensed. Further, the aliphatic polyester resin (A) of the present invention may contain one kind of the aliphatic hydroxycarboxylic acid unit (3) alone, or may contain two kinds or more in any ratio and combination. .

The aliphatic hydroxycarboxylic acid unit (3) is optional as long as it is a unit derived from an aliphatic hydroxycarboxylic acid containing R ³ having a carbon number in the range described above and / or a derivative thereof.

  The aliphatic hydroxycarboxylic acid unit (3) used in the present invention is an aliphatic hydroxycarboxylic acid and / or a derivative thereof (hereinafter collectively referred to as “aliphatic hydroxycarboxylic acid component (3)” as appropriate. ). As long as the aliphatic hydroxycarboxylic acid component (3) is an aliphatic compound or alicyclic compound having two carboxyl groups and one hydroxyl group, it is optional as long as the effects of the present invention are not significantly impaired. Specific examples of the aliphatic hydroxycarboxylic acid include malic acid, hydroxyglutaric acid, hydroxymethylglutaric acid and the like. Examples of the aliphatic hydroxycarboxylic acid derivatives include lower alkyl esters of the above aliphatic hydroxycarboxylic acids. Among these, malic acid is preferable as the aliphatic hydroxycarboxylic acid, and ethyl ester of malic acid is preferable as the derivative of the aliphatic hydroxycarboxylic acid. Furthermore, as the aliphatic hydroxycarboxylic acid component (3), a mixture of malic acid and malic acid ethyl ester is also preferred. As the aliphatic hydroxycarboxylic acid component (3), one type may be used alone, or two or more types may be used in optional ratio and combination.

  The amount of the aliphatic hydroxycarboxylic acid unit (3) contained in the aliphatic polyester resin (A) of the present invention is polyester from the viewpoint that the aliphatic polyester resin (A) having a high degree of polymerization can be easily produced. Is usually 0.00050 mol% or more, preferably 0.0050 mol% or more, more preferably 0.020 mol% or more, still more preferably 0.040 mol%, based on 100 mol% of the total amount of all units constituting Above, especially preferably 0.075 mol% or more. In addition, the upper limit is usually less than 0.450 mol%, preferably 0.25 mol% or less, more preferably 0.18 mol% or less, and still more preferably, from the viewpoint of the possibility of causing the generation of gel. It is 0.13 mol% or less, Most preferably, it is 0.10 mol% or less. If the amount of the aliphatic hydroxycarboxylic acid unit (3) contained is too small, the melt tension at the time of sheet molding or secondary processability may be insufficient, and if too much, gelation may be caused. is there.

The amount of the aliphatic hydroxycarboxylic acid unit (3) contained in the aliphatic polyester resin (A) can be measured, for example, in the same manner as in the case of the aliphatic dicarboxylic acid unit (1). Specifically, for example, the aliphatic hydroxycarboxylic acid unit (3) provided by malic acid is a fatty acid that appears in the vicinity of 5.47 ppm when the hydroxyl group of the unit forms an ester bond to form a branched chain. It can be quantified by the peak of the methine proton of the group hydroxycarboxylic acid unit (3). On the other hand, when the hydroxyl group of the unit is unreacted, it can be quantified by the peak of the methine proton of the aliphatic hydroxycarboxylic acid unit (3) appearing around 4.49 ppm. In this case, the sample preparation conditions and the ¹ H-NMR measurement conditions are not particularly limited as long as the aliphatic hydroxycarboxylic acid units (3) can be suitably quantified. For example, the aliphatic dicarboxylic acid units ( By following the conditions for determining the amount of 1), the aliphatic hydroxycarboxylic acid unit (3) can be quantified.

Further, in the aliphatic polyester resin (A) of the present invention, in addition to the units derived from the above-mentioned aliphatic hydroxycarboxylic acid component (3), an aromatic hydroxycarboxylic acid is used unless the effects of the present invention are significantly impaired. And / or derivatives thereof (hereinafter collectively referred to as “aromatic hydroxycarboxylic acid component (3)” as appropriate) (hereinafter referred to as “aromatic hydroxycarboxylic acid unit (3)” as appropriate). May be included in any ratio and combination. Specific examples of the aromatic hydroxycarboxylic acid include hydroxyisophthalic acid and hydroxyterephthalic acid. Specific examples of the aromatic hydroxycarboxylic acid derivative include methyl ester, ethyl ester and propyl ester of the aromatic dicarboxylic acid. And lower alkyl esters such as butyl esters. Among these, hydroxyisophthalic acid and hydroxyterephthalic acid are preferable. As the aromatic hydroxycarboxylic acid component (3), one kind may be used alone, and two kinds or more may be used in optional ratio and combination.

(Aliphatic hydroxycarboxylic acid unit represented by formula (4))
In the present invention, R ⁴ of the aliphatic hydroxycarboxylic acid unit represented by the above formula (4) (hereinafter referred to as “aliphatic hydroxycarboxylic acid unit (4)” as appropriate) usually has 1 or more carbon atoms. The aliphatic hydrocarbon group is preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less from the viewpoint of availability. R ⁴ may be a chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, which is a combination of a chain aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group. May be. In the case of a chain aliphatic hydrocarbon group, it may be a linear aliphatic hydrocarbon group or a branched chain aliphatic hydrocarbon group. In the case of a cycloaliphatic hydrocarbon group, it may be a single ring, or may be one in which a plurality of rings are bonded to each other or condensed. Further, the aliphatic polyester resin (A) of the present invention may contain one kind of the aliphatic hydroxycarboxylic acid unit (4) alone, or may contain two kinds or more in any ratio and combination. .

The aliphatic hydroxycarboxylic acid unit (4) is optional as long as it is a unit derived from an aliphatic hydroxycarboxylic acid containing R ⁴ having a carbon number in the range described above and / or a derivative thereof.

  The aliphatic hydroxycarboxylic acid unit (4) used in the present invention is derived from an aliphatic hydroxycarboxylic acid and / or a derivative thereof (hereinafter referred to as “aliphatic hydroxycarboxylic acid component (4)” as appropriate). is there. The aliphatic hydroxycarboxylic acid component (4) is optional as long as it does not significantly impair the effects of the present invention as long as it is an aliphatic compound and an alicyclic compound having three carboxyl groups and one hydroxyl group. Specific examples of the aliphatic hydroxycarboxylic acid include citric acid and isocitric acid. Specific examples of the aliphatic hydroxycarboxylic acid derivatives include lower alkyl esters such as methyl ester, ethyl ester, propyl ester, and butyl ester of the above aliphatic carboxylic acid, disodium hydrogen citrate, sodium citrate, and citric acid. Examples thereof include metal salts of the above aliphatic hydroxycarboxylic acids such as potassium. Among these, as the aliphatic hydroxycarboxylic acid, citric acid is preferable, and as the derivative of the aliphatic hydroxycarboxylic acid, ethyl ester of citric acid, butyl ester of citric acid, or a mixture thereof is preferable. As the aliphatic hydroxycarboxylic acid component (4), one kind may be used alone, and two kinds or more may be used in optional ratio and combination.

The amount of the aliphatic hydroxycarboxylic acid unit (4) contained in the aliphatic polyester resin (A) of the present invention is polyester from the viewpoint that the aliphatic polyester resin (A) having a high degree of polymerization can be easily produced. Is usually 0.00050 mol% or more, preferably 0.0050 mol% or more, more preferably 0.020 mol% or more, still more preferably 0.040 mol%, based on 100 mol% of the total amount of all units constituting Above, especially preferably 0.075 mol% or more. In addition, the upper limit is usually less than 0.450 mol%, preferably 0.25 mol% or less, more preferably 0.18 mol% or less, and still more preferably, from the viewpoint of the possibility of causing the generation of gel. 0.13 mol% or less, particularly preferably 0.10 mol% or less. When the amount of the aliphatic hydroxycarboxylic acid unit (4) contained is too small, the resin composition (A ′) is laminated on the substrate to produce a biodegradable laminated sheet, and at the time of sheet molding or secondary processability. In some cases, the melt tension is insufficient, and if it is too much, gelation may be caused.

  Furthermore, the reason why the unit derived from malic acid as the aliphatic hydroxycarboxylic acid unit (3) and / or the unit derived from citric acid as the aliphatic hydroxycarboxylic acid unit (4) is particularly preferred is, for example, malic acid And / or by using citric acid as the aliphatic hydroxycarboxylic acid component, malic acid and / or citric acid causes a dehydration reaction to form a double bond in the aliphatic polyester resin (A), Group unsaturated dicarboxylic acid units can be formed.

The amount of the aliphatic hydroxycarboxylic acid unit (4) contained in the aliphatic polyester resin (A) can be measured, for example, in the same manner as in the case of the aliphatic dicarboxylic acid unit (1). Specifically, for example, in the case of the aliphatic hydroxycarboxylic acid unit (4) derived from citric acid, when the hydroxyl group of the unit forms an ester bond to form a branched chain, 3.18 ppm to 3.36 ppm It can be quantified by the methylene proton peak of the aliphatic hydroxycarboxylic acid unit (4) appearing in the vicinity. On the other hand, when the hydroxyl group of the unit is unreacted, it can be quantified by the methylene proton peak of the aliphatic hydroxycarboxylic acid unit (4) appearing in the vicinity of 2.87 ppm to 2.91 ppm. In this case, sample preparation conditions and ¹ H-NMR measurement conditions are not particularly limited as long as the aliphatic hydroxycarboxylic acid units (4) can be suitably quantified. For example, aliphatic dicarboxylic acid units ( By following the conditions for quantifying the amount of 1), the aliphatic hydroxycarboxylic acid unit (4) can be quantified.

(Aliphatic unsaturated dicarboxylic acid unit represented by formula (5))
In the present invention, R ⁵ of the aliphatic unsaturated dicarboxylic acid unit represented by the above formula (5) (hereinafter appropriately referred to as “aliphatic unsaturated dicarboxylic acid unit (5)”) is one or more. An aliphatic hydrocarbon group having a double bond and usually having 2 or more carbon atoms, usually 20 or less, preferably 10 or less, more preferably 6 or less, and further preferably 3 or less from the viewpoint of availability. is there. The aliphatic hydrocarbon group may be a chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, and the chain aliphatic hydrocarbon group and the cyclic aliphatic hydrocarbon group are bonded to each other. It may be a thing. In the case of a chain aliphatic hydrocarbon group, it may be a linear aliphatic hydrocarbon group or a branched chain aliphatic hydrocarbon group. In the case of a cycloaliphatic hydrocarbon group, it may be a single ring, or may be one in which a plurality of rings are bonded to each other or condensed. Moreover, the aliphatic polyester resin (A) of the present invention may contain one kind of the aliphatic unsaturated dicarboxylic acid unit (5) alone, or may contain two kinds or more in any ratio and combination. good.

  In order for the aliphatic polyester resin of the present invention to be a resin having sufficient melt tension at the time of sheet molding and better moldability than before, the aliphatic unsaturated dicarboxylic acid unit (5) and the aliphatic unsaturated resin described later are used. It is important that the saturated dicarboxylic acid units (6) and (7) are included in the aliphatic polyester resin of the present invention in optimum amounts. The reason for this is not clear yet, but is presumed as follows.

  When forming a sheet, the carbon atom constituting the double bond of these aliphatic unsaturated dicarboxylic acid units is a radical reaction between the double bond and an inorganic peroxide, an organic peroxide (B) or an organic azo compound. Initiator, other free radicals, or ion radicals react with each other, or are induced by heat, and have characteristics that can become radical centers. That is, the radical generated on the carbon atom constituting the double bond has a characteristic that a branched chain is formed by a subsequent reaction with surrounding organic substances. When such a unit having a double bond is contained as an aliphatic polyester constituent unit, an appropriate amount of branched chain can be effectively generated in the resin. Therefore, the aliphatic polyester resin of the present invention ( A) is excellent in melt tension and has characteristics that allow fine adjustment of the melt tension.

The amount of the double bond of the R ^5, when the number of carbon atoms of the R ⁵ and r, if r is an even number, usually 1 or more, the upper limit is usually r / 2 or less. On the other hand, when r is an odd number (r is 3 or more), it is usually 1 or more, and its upper limit is usually (r-1) / 2 or less. However, when there are too many double bonds, gelation may be caused as a result of the generation of many cross-links involving the carbon atom serving as the radical center. Therefore, the upper limit of the amount of double bonds is preferably 2 or less.

The aliphatic unsaturated dicarboxylic acid unit (5) is optional as long as it is a unit derived from an aliphatic unsaturated dicarboxylic acid containing R ⁵ and / or a derivative thereof having carbon number in the above-mentioned range.

  The aliphatic unsaturated dicarboxylic acid unit (5) used in the present invention is derived from an aliphatic unsaturated dicarboxylic acid and / or a derivative thereof (hereinafter referred to as “aliphatic unsaturated dicarboxylic acid component (5)” as appropriate). To do. Specific examples of the aliphatic unsaturated dicarboxylic acid component (5) include the aliphatic unsaturated dicarboxylic acid component (8) and the aliphatic unsaturated dicarboxylic acid component (9) described below.

  The aliphatic unsaturated dicarboxylic acid unit (5) is optional as long as the effects of the present invention are not significantly impaired. For example, the aliphatic unsaturated dicarboxylic acid represented by the following formula (8) and / or formula (9): Examples include units.

（式（８）及び式（９）は、ともに二重結合に関する幾何異性体であって、式（８）はトランス型、式（９）はシス型を表す。ｍ及びｎは、それぞれ独立に、０〜１８の整数を表す。Ｒ⁶及びＲ⁷は、それぞれ独立に、水素又は炭素数が１〜１８の脂肪族炭化水素基を表す。）

(Formula (8) and Formula (9) are both geometrical isomers relating to a double bond, wherein Formula (8) represents a trans form, and Formula (9) represents a cis form. And represents an integer of 0 to 18. R ⁶ and R ⁷ each independently represents hydrogen or an aliphatic hydrocarbon group having 1 to 18 carbon atoms.

Aliphatic unsaturated dicarboxylic acid units represented by the above formulas (8) and (9) (hereinafter referred to as “aliphatic unsaturated dicarboxylic acid units (8)” and “aliphatic unsaturated dicarboxylic acid units ( 9) ") and R ⁶ and R ⁷ in (1) are each independently hydrogen or carbon number is usually 1 or more, and usually 18 or less, preferably 15 or less, more preferably 10 or less, still more preferably It represents an aliphatic hydrocarbon group of 5 or less, particularly preferably 2 or less. When there are too many carbon atoms, the circumference | surroundings of a double bond become bulky, Therefore The reactivity of a double bond falls, a radical center is not produced | generated, and the said branched chain may become difficult to generate | occur | produce. The aliphatic hydrocarbon group may be a chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, and the chain aliphatic hydrocarbon group and the cyclic aliphatic hydrocarbon group are bonded to each other. It may be a thing. In the case of a chain aliphatic hydrocarbon group, it may be a linear aliphatic hydrocarbon group or a branched chain aliphatic hydrocarbon group. In the case of a cycloaliphatic hydrocarbon group, it may be a single ring, or may be one in which a plurality of rings are bonded to each other or condensed. Moreover, the aliphatic polyester resin (A) of the present invention may contain one kind of each of the aliphatic unsaturated dicarboxylic acid units (8) and (9), and each of them may contain two or more kinds in any ratio. And may be included in combination.

R ⁶ and R ⁷ may be bonded directly or via another functional group or atom to form a ring.

  Further, in the above formulas (8) and (9), m represents the number of methylene groups, and is usually 0 or more, and the upper limit is usually 18 or less, preferably 15 or less, more preferably 10 or less, still more preferably. Is 5 or less, particularly preferably 2 or less. When the number of methylene groups is too large, it may be difficult to obtain the aliphatic hydroxycarboxylic acid component (8) and / or (9), and it occurs between molecular chains in the aliphatic polyester resin (A). As a result of suppressing the formation of crystals, the heat resistance of the aliphatic polyester resin (A) may be lowered.

  Moreover, in said Formula (8) and Formula (9), n represents the number of a methylene group similarly to said m. n is arbitrary as long as the effects of the present invention are not significantly impaired, but it is preferable that n is satisfied.

  The aliphatic unsaturated dicarboxylic acid unit (5) is a trans unsaturated aliphatic dicarboxylic acid unit (8) and / or a cis aliphatic unsaturated dicarboxylic acid unit ( 9) is preferable. The molar ratio of the aliphatic unsaturated dicarboxylic acid unit (8) to the aliphatic unsaturated dicarboxylic acid unit (9) is expressed as {number of moles of aliphatic unsaturated dicarboxylic acid unit (8)} / {aliphatic unsaturated dicarboxylic acid unit. When the number of moles of (9) is defined, the ratio is within the specific range described below, so that the aliphatic polyester resin (A) of the present invention has excellent melt tension and a desired melt tension. Fine adjustment is possible.

  Here, the specific range is usually 0.5 or more, preferably 0.8 or more, more preferably 1.0 or more, still more preferably 1.2 or more, and particularly preferably 1.5 or more. Moreover, the upper limit is 8.5 or less normally, Preferably it is 7.5 or less, More preferably, it is 6.5 or less, More preferably, it is 5.5 or less, Most preferably, it is 4.5 or less. When the above molar ratio does not satisfy this range, the resin composition (A ′) may have poor melt tension or it may be difficult to finely adjust the melt tension.

In addition, the amount of the aliphatic unsaturated dicarboxylic acid units (8) and (9) contained in the aliphatic polyester resin (A) can be measured in the same manner as in the case of the aliphatic dicarboxylic acid unit, for example. Specifically, for example, when the aliphatic hydroxycarboxylic acid unit (8) is a unit derived from fumaric acid, a double bond in the fumaric acid unit appearing in the vicinity of 6.85 ppm of ¹ H-NMR is formed. It can be quantified by the proton peak on the carbon atom. Further, for example, as the aliphatic hydroxycarboxylic acid unit (9), in the case of a unit derived from maleic acid, ¹
This can be quantified by the proton peak on the carbon atom forming a double bond in the maleic acid unit appearing around 6.25 ppm in H-NMR. In this case, the sample preparation conditions and the ¹ H-NMR measurement conditions are not particularly limited as long as the aliphatic unsaturated dicarboxylic acid units (8) and (9) can be suitably quantified. The aliphatic unsaturated dicarboxylic acid units (8) and (9) are obtained by following the conditions for quantifying the amount of the aliphatic dicarboxylic acid unit (1).
Can be quantified.

As long as the aliphatic unsaturated dicarboxylic acid units (8) and (9) are units derived from aliphatic unsaturated dicarboxylic acid units and / or derivatives thereof containing R ⁶ and R ⁷ having the carbon number in the range described above. Is optional.

  The aliphatic unsaturated dicarboxylic acid unit (8) is usually referred to as “aliphatic unsaturated dicarboxylic acid component (8)” as appropriate. ). Specific examples of the aliphatic unsaturated dicarboxylic acid component (8) are preferably fumaric acid, monoethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate or a mixture thereof. , Fumaric acid, monoethyl fumarate, diethyl fumarate or a mixture thereof is more preferable, and fumaric acid is particularly preferable. As the aliphatic unsaturated dicarboxylic acid component (8), one type may be used alone, or two or more types may be used in optional ratio and combination.

  The aliphatic unsaturated dicarboxylic acid unit (9) is usually referred to as an “aliphatic unsaturated dicarboxylic acid component (9)” as appropriate. ). Specific examples of the aliphatic unsaturated dicarboxylic acid component (9) include maleic acid, monoethyl maleate, mono n-butyl maleate, mono 2-ethylhexyl maleate, diethyl maleate, di-n-butyl maleate, maleic acid Di2-ethylhexyl or a mixture thereof is preferable, maleic acid, monoethyl maleate, diethyl maleate or a mixture thereof is more preferable, and maleic acid is particularly preferable. As the aliphatic unsaturated dicarboxylic acid component (9), one type may be used alone, or two or more types may be used in optional ratio and combination.

  Accordingly, the aliphatic unsaturated dicarboxylic acid unit (5) is particularly preferably a unit derived from fumaric acid and / or maleic acid.

  The amount of the aliphatic unsaturated dicarboxylic acid unit (5) contained in the aliphatic polyester resin (A) of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is included in the aliphatic polyester resin (A). Is usually 0.00015 mol% or more, preferably 0.0050 mol% or more, more preferably 0.010 mol% or more, still more preferably 0.015 mol% or more, based on 100 mol% of the total amount of all units to be obtained. Particularly preferred is 0.025 mol% or more, and the upper limit thereof is usually 0.25 mol% or less, preferably 0.18 mol% or less, more preferably 0.058 mol% or less, still more preferably 0.048 mol%. The mol% or less, particularly preferably 0.038 mol% or less. If the amount contained is too small, it may be difficult to effectively generate a branched chain. If it is too large, the branched chain tends to be excessively generated, and the melt viscosity of the resin composition (A ′) is finely adjusted. May be difficult.

The amount of the aliphatic unsaturated dicarboxylic acid unit (5) contained in the aliphatic polyester resin (A) can be measured, for example, in the same manner as in the case of the aliphatic dicarboxylic acid unit (1). Specifically, for example, when ¹ H-NMR similar to the case where the amount of the aliphatic dicarboxylic acid unit (1) is measured, a proton on a carbon atom forming a double bond, or the carbon It can be measured by a peak derived from a proton on a carbon atom that is directly chemically bonded to the atom. In this case, the sample preparation conditions and ¹ H-NMR measurement conditions are not particularly limited as long as the aliphatic unsaturated dicarboxylic acid unit (5) can be suitably quantified. For example, the aliphatic dicarboxylic acid unit By following the conditions for quantifying the amount of (1), the aliphatic unsaturated dicarboxylic acid unit (5) can be quantified.

In the aliphatic polyester resin (A) of the present invention, the aliphatic hydroxycarboxylic acid units (3) and (4), the aliphatic unsaturated dicarboxylic acid unit (5), and the aliphatic unsaturated dicarboxylic acid unit (6 ) And (7) is usually 0.0010 mol% or more, preferably 0.010 mol% or more, more preferably 0.000 mol% or more with respect to 100 mol% in total of all units contained in the aliphatic polyester resin. 020 mol% or more, more preferably 0.030 mol% or more, particularly preferably 0.050 mol% or more, and the upper limit is usually 0.50 mol% or less, preferably 0.30 mol% or less, more preferably Is 0.20 mol% or less, more preferably 0.15 mol% or less, and particularly preferably 0.12 mol% or less. When the total amount is too small, the resin composition (A ′) is laminated on a base material to produce a biodegradable laminated sheet, and the melt tension is insufficient at the time of sheet molding or secondary workability, It may be difficult to finely adjust the melt tension appropriately and easily. On the other hand, if the total amount is too large, it may be difficult to finely adjust the melt tension of the resin composition (A ′) or may cause gelation.

  Furthermore, the aliphatic hydroxycarboxylic acid unit (3) and the aliphatic hydroxycarboxylic acid unit relative to the total of the aliphatic unsaturated dicarboxylic acid unit (5) and the aliphatic unsaturated dicarboxylic acid units (6) and (7) described later The total molar ratio of (4) is {the total number of moles of aliphatic hydroxycarboxylic acid units (3) and the number of moles of aliphatic hydroxycarboxylic acid units (4)} / {aliphatic unsaturated dicarboxylic acid units (5 ) And the sum of the number of moles of the aliphatic unsaturated dicarboxylic acid units (6) and (7) described below}, this ratio is usually 1.0 or more, preferably 1.2 or more, more preferably 1.5 or more, more preferably 1.8 or more, particularly preferably 2.0 or more, and the upper limit thereof is usually 7.0 or less, preferably 5.0 or less, more preferably 4.0 or less, still more preferably Is 3. Or less, particularly preferably of 3.0 or less. In the aliphatic polyester resin (A) of the present invention, the aliphatic hydroxycarboxylic acid units (3) and (4) capable of generating a branched chain by forming an ester bond, and the double chain to the branched chain by the above mechanism. By adjusting the content of the aliphatic unsaturated dicarboxylic acid units (5), (6) and (7) in the aliphatic polyester resin (A) to the specific ratio described above, when forming a sheet Thus, it is possible to provide a resin composition (A ′) that is excellent in the melt tension and can finely adjust the melt tension. Therefore, even if the ratio is too small or too large, the melt tension is inadequate during sheet forming or secondary processing when the biodegradable laminated sheet is produced by laminating the resin composition (A ′) on the base material. It may be sufficient, or it may be difficult to finely adjust the melt tension effectively and easily.

  In the present invention, the aliphatic unsaturated dicarboxylic acid unit (5) is derived from an aliphatic hydroxycarboxylic acid component (3) used as a raw material for producing an aliphatic polyester by a dehydration reaction as shown in the examples of the present invention. May be.

(Aliphatic unsaturated dicarboxylic acid unit represented by formula (6) or formula (7))
In order for the resin composition (A ′) of the present invention to have sufficient melt tension at the time of sheet molding and to have better moldability than before, the aliphatic polyester resin (A) of the present invention comprises the above structural units. It is important to include in the above proportion. However, the aliphatic polyester resin (A) of the present invention is an aliphatic unsaturated dicarboxylic acid represented by the above formula (6) from the viewpoint that it is a unit having a double bond unless the effects of the present invention are significantly impaired. An acid unit (hereinafter referred to as “aliphatic unsaturated dicarboxylic acid unit (6)” as appropriate) or an aliphatic unsaturated dicarboxylic acid unit represented by formula (7) (hereinafter referred to as “aliphatic unsaturated dicarboxylic acid unit as appropriate”) (7) ") may be included. The aliphatic unsaturated dicarboxylic acid unit (6) and / or (7) may be included together with the aliphatic unsaturated dicarboxylic acid unit (5), and included in place of the aliphatic unsaturated dicarboxylic acid unit (5). It may be.
When the aliphatic unsaturated dicarboxylic acid unit (6) and / or (7) is contained in the aliphatic polyester resin (A) instead of the aliphatic unsaturated dicarboxylic acid unit (5), the aliphatic unsaturated dicarboxylic acid contained therein The total amount of the acid units (6) and / or (7) satisfies the amount of the aliphatic unsaturated dicarboxylic acid unit (5) contained in the aliphatic polyester resin (A). Further, when the aliphatic polyester resin (A) includes the aliphatic unsaturated dicarboxylic acid unit (5) and the aliphatic unsaturated dicarboxylic acid units (6) and (7), the total amount of these three units is: The amount of the aliphatic unsaturated dicarboxylic acid unit (5) contained in the aliphatic polyester resin (A) is satisfied.

R ^{8 of the} aliphatic unsaturated dicarboxylic acid unit (6) and the aliphatic unsaturated dicarboxylic acid unit (7)
Are each independently hydrogen or carbon number is usually 1 or more, and the upper limit thereof is usually 17 or less, preferably 14 or less, more preferably 9 or less, still more preferably 4 or less, particularly preferably 2 or less. Represents an aliphatic hydrocarbon group. When the number of carbon atoms is too large, the periphery of the double bond becomes bulky, so that the reactivity of the double bond is lowered and it may be difficult to generate a branched chain. The aliphatic hydrocarbon group may be a chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, and the chain aliphatic hydrocarbon group and the cyclic aliphatic hydrocarbon group are bonded to each other. It may be a thing. In the case of a chain aliphatic hydrocarbon group, it may be a linear aliphatic hydrocarbon group or a branched chain aliphatic hydrocarbon group. In the case of a cycloaliphatic hydrocarbon group, it may be a single ring, or may be one in which a plurality of rings are bonded to each other or condensed. Each of the aliphatic unsaturated dicarboxylic acid units (6) and (7) may be contained alone in the aliphatic polyester resin (A) of the present invention, and the ratio of the two or more types may be selected. It may be included in combination.

R ⁸ may be bonded directly or through another functional group or atom to form a ring.

  Further, in the above formulas (6) and (7), r represents the number of methylene groups, and is usually 0 or more, and the upper limit thereof is usually 17 or less, preferably 14 or less, more preferably 9 or less, still more preferably. Is 4 or less, particularly preferably 2 or less. When the number of methylene groups is too large, it may be difficult to obtain the aliphatic dicarboxylic acid component (6) and / or (7), and crystals formed between molecular chains in the aliphatic polyester resin (A). As a result, the heat resistance of the aliphatic polyester resin (A) may be lowered.

  Moreover, in said Formula (6) and Formula (7), s represents the number of methylene groups similarly to said r. s is optional as long as the effects of the present invention are not significantly impaired, but it is preferable to satisfy the preferable range of r.

  Specific examples of the aliphatic unsaturated dicarboxylic acid component (6) that gives the aliphatic unsaturated dicarboxylic acid unit (6) include trans-aconitic acid. Specific examples of the aliphatic unsaturated dicarboxylic acid component (7) that gives the aliphatic unsaturated dicarboxylic acid unit (7) include cis-aconitic acid and aconitic acid anhydride. Of these, cis-aconitic acid is preferred. As the aliphatic unsaturated dicarboxylic acid components (6) and (7), one kind may be used alone, and two kinds or more may be used in optional ratio and combination.

  In the present invention, the aliphatic unsaturated dicarboxylic acid units (6) and (7) are derived from the aliphatic hydroxycarboxylic acid component (3) and / or (4) used as a raw material for the aliphatic polyester resin by a dehydration reaction. May be.

  The molar ratio of the aliphatic unsaturated dicarboxylic acid unit (6) to the aliphatic unsaturated dicarboxylic acid unit (7) is expressed as {number of moles of aliphatic unsaturated dicarboxylic acid unit (6)} / {aliphatic unsaturated dicarboxylic acid unit. When the number of moles of (7) is defined, by setting the ratio within the specific range described below, the resin composition (A ′) of the present invention is excellent in melt tension and has a desired melt tension. Fine adjustment is possible.

Here, the specific range is usually 0.5 or more, preferably 0.8 or more, more preferably 1.0 or more, still more preferably 1.2 or more, and particularly preferably 1.5 or more. Moreover, the upper limit is 8.5 or less normally, Preferably it is 7.5 or less, More preferably, it is 6.5 or less, More preferably, it is 5.5 or less, Most preferably, it is 4.5 or less. When the above molar ratio does not satisfy this range, the resin composition (A ′) may have poor melt tension or it may be difficult to finely adjust the melt tension.

The amount of the aliphatic unsaturated dicarboxylic acid unit (6) and / or (7) contained in the aliphatic polyester resin (A) is, for example, the same method as in the case of the aliphatic dicarboxylic acid unit (1). To measure. Specifically, for example, it is quantified or measured by a peak derived from a proton on a carbon atom forming a double bond or a proton on a carbon atom directly bonded to the carbon atom by ¹ H-NMR. It can be quantified using an easy proton peak. For example, in the case of a unit derived from trans-aconitic acid, it can be quantified by a peak appearing in the vicinity of 6.93 ppm using ¹ H-NMR. In this case, the sample preparation conditions and ¹ H-NMR measurement conditions are not particularly limited as long as the aliphatic unsaturated dicarboxylic acid units (6) and / or (7) can be suitably quantified. The aliphatic unsaturated dicarboxylic acid unit (6) and / or (7) can be quantified by following the conditions in which the amount of the aliphatic dicarboxylic acid unit (1) is quantified.

[1-2. Preferred embodiment of each structural unit contained in aliphatic polyester resin (A) of the present invention]
The aliphatic polyester resin (A) of the present invention has the above units in the above amounts. Accordingly, the aliphatic polyester resin (A) of the present invention is sufficiently high molecular weight without using chain extenders such as isocyanate compounds and carbonates, sufficiently suppressing the occurrence of blistering due to gelation and the like. In addition, it has characteristics such as excellent formability such as mechanical properties such as tensile properties. Furthermore, it is preferable that the amount of each unit contained in the aliphatic polyester resin (A) of the present invention satisfies the range of the following formula (10). When the amount of each unit contained in the aliphatic polyester resin (A) satisfies the following formula, the aliphatic polyester resin (A) is used for sheet molding such as general-purpose plastic molding such as injection molding, hollow molding, and extrusion molding. Aliphatic polyester that has excellent moldability because of sufficient melt tension during secondary processing such as vacuum forming, and can suppress the occurrence of fluff due to gelation during sheet forming, so there is no poor appearance due to blisters Resin (A) can be provided.

It is preferable that each unit contained in the aliphatic polyester resin (A) of the present invention satisfies the range described by the following formula (10).
[{X- (A + T + S)} / X] / 100 (10)
(In the formula (10), X represents the aliphatic hydroxycarboxylic acid components (3) and (4) contained in the raw material with respect to the total amount of 100 mol% of all units contained in the aliphatic polyester resin (A). The compounds shown above which give the aliphatic hydroxycarboxylic acid units (3) and (4) represented, and the aliphatic unsaturation represented by the above formulas (6), (7), (8) and (9) Represents the ratio (mol%) of the total number of moles of the above-mentioned compounds giving the dicarboxylic acid unit, where A is the aliphatic polyester resin relative to 100 mol% of the total amount of all units contained in the aliphatic polyester resin (A). Ratio of the total number of moles of the aliphatic hydroxycarboxylic acid unit represented by the above formula (3) and / or the aliphatic hydroxycarboxylic acid unit represented by the above formula (4) in the structural unit of (A) (mol%) ) T represents The ratio (mol%) of the number of moles of the aliphatic unsaturated dicarboxylic acid units represented by the above formulas (6) and (8) with respect to 100 mol% of the total amount of all units contained in the aliphatic polyester resin (A). S represents the fat represented by the above formula (7) and formula (9) contained in the aliphatic polyester resin (A) with respect to 100 mol% of the total amount of all units contained in the aliphatic polyester resin (A). Represents the proportion (mol%) of the group unsaturated dicarboxylic acid unit.

The aliphatic polyester resin (A) of the present invention is excellent in melt tension, can finely adjust the melt tension, has excellent moldability than before, and sufficiently gelates during sheet molding. In order to be an aliphatic polyester resin (A) that can be suppressed and the molded product does not have a poor appearance due to lumps, the value of [{X− (A + T + S)} / X] in the above formula (10) is usually 1.0. Or more, preferably 5.0 or more, more preferably 10 or more, still more preferably 20 or more, particularly preferably 25 or more, and the upper limit is usually less than 100, preferably 80 or less, more preferably 60 or less, further Preferably it is 50 or less, still more preferably 35 or less, particularly preferably 31 or less.

  The aliphatic polyester resin (A) provided in the present invention is excellent in melt tension, can finely adjust the melt tension, and has excellent moldability as compared with the conventional gelation during sheet molding. Therefore, the above formula (10) preferably satisfies the above range in order to be an aliphatic polyester resin (A) in which the molded product can be sufficiently suppressed and the appearance does not have poor appearance due to bumps. When the above formula (10) satisfies the above range, the melt tension is excellent and the melt tension can be finely adjusted. In addition to the excellent moldability as compared with the conventional method, the gelation at the time of sheet molding is sufficient. The reason why the molded product is an aliphatic polyester resin (A) having no appearance defect due to lumps is not yet clear, but is presumed as follows.

  First, X which is a denominator in the above formula (10) is an unbranched ester bond as a raw material necessary for producing the aliphatic polyester resin (A) before producing the aliphatic polyester resin (A). It is the total of the number of compounds giving a tri- or higher functional hydroxycarboxylic acid unit capable of generating a branched chain and the number of compounds giving the above aliphatic unsaturated dicarboxylic acid unit capable of generating a branched chain from a double bond. {X- (A + T + S)}, which is a molecule in the above formula (10), is derived from the above formula (3) and the above formula (4) from the number of compounds (X) as the raw material that was unbranched before resin production. And the number of aliphatic unsaturated dicarboxylic acid units represented by the above formulas (6), (7), (8) and (9). That is, {X− (A + T + S)} represents a part of the compound having a double bond that gives an aliphatic unsaturated dicarboxylic acid unit before the production of the aliphatic polyester resin (A). It is the number of units present in the aliphatic polyester resin (A) as a constituent unit by losing the double bond in the process of providing the provided aliphatic polyester resin (A).

  That is, the double bond disappears by the subsequent reaction with the surrounding organic matter or the like due to the participation of radicals induced by heat or the like at the time of heating such as production, and a part of these subsequent reactions are aliphatic polyester resin (A) It is thought that a branched chain was formed inside. That is, the higher the value of [{X− (A + T + S)} / X], the greater the number of branched chains and the higher the possibility of gelation. On the other hand, when the value is too small, the possibility of gelation is reduced from the viewpoint of suppressing gelation.

[1-3. Other structural units]
The aliphatic polyester resin (A) of the present invention has the above aliphatic dicarboxylic acid unit (1), aliphatic diol unit (2), and aliphatic hydroxycarboxylic acid unit (3) unless the effects of the present invention are significantly impaired. And / or (4) one or more aliphatic unsaturated dicarboxylic acid units selected from the group consisting of aliphatic unsaturated dicarboxylic acid units (5), (6), (7), (8) (hereinafter these May be included in addition to the structural unit of “essential unit”), and may include other structural units (hereinafter referred to as “arbitrary unit” as appropriate). Especially, it is preferable to contain the structural unit which the following polyfunctional components give by arbitrary ratios and combinations. However, even in that case, the content of the structural unit satisfies the above range.

Specific examples of the polyfunctional component include a bifunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polyvalent carboxylic acid, a trifunctional or higher polyvalent carboxylic acid anhydride. Etc. The aliphatic polyester resin (A) containing a unit given by these polyfunctional components (hereinafter referred to as “polyfunctional unit” as appropriate) tends to easily have a high degree of polymerization. Among them, the aliphatic polyester resin (A) of the present invention may preferably contain a unit derived from a bifunctional oxycarboxylic acid, and the aliphatic polyester resin (A) without using a chain extender described later. Derived from one or more components selected from the group consisting of a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid, and a trifunctional or higher polyhydric carboxylic acid anhydride It may be more preferable to include the unit to do. In addition, a polyfunctional component may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

  Specific examples of the bifunctional oxycarboxylic acid include lactic acid, glycolic acid, hydroxybutyric acid, hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, and 2-hydroxyisocaproic acid. , Caprolactone, and the like. These may be oxycarboxylic acid esters or lactones, or oxycarboxylic acid polymer derivatives. Among these, lactic acid and glycolic acid are preferable from the viewpoint of easy availability. Moreover, as the form, 30 to 95 weight% of aqueous solution is preferable from a viewpoint that acquisition is easy. Further, when optical isomers are present in these, any of D-form, L-form, and racemate may be used, and the form may be a solution such as a solid, a liquid, or an aqueous solution.

  The amount of the bifunctional oxycarboxylic acid unit is usually 0.02 mol% or more, preferably 0.5 mol, based on 100 mol% of the total amount of all units constituting the aliphatic polyester resin (A). It is at least mol%, more preferably at least 1.0 mol%. On the other hand, the upper limit of the amount used is usually 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less. When the aliphatic polyester resin (A) of the present invention is produced, the polymerization degree of the aliphatic polyester resin (A) of the present invention can be increased by using the above components in the above amounts.

Specific examples of the trifunctional or higher polyhydric alcohol include glycerin, trimethylolpropane, pentaerythritol and the like.
Specific examples of the trifunctional or higher polyvalent carboxylic acid and the trifunctional or higher polyvalent carboxylic acid anhydride include propanetricarboxylic acid, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, cyclopentatetracarboxylic anhydride, and the like. Can be mentioned.

  One or more selected from the group consisting of a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid, and a trifunctional or higher polycarboxylic acid anhydride contained in the aliphatic polyester resin (A) of the present invention. The amount of the unit derived from the polyfunctional component is usually 0.0001 mol% or more, preferably 0.001 mol% or more with respect to 100 mol% of the total amount of all units constituting the aliphatic polyester resin (A). More preferably, it is 0.005 mol% or more, and particularly preferably 0.01 mol% or more. The upper limit is usually 5 mol% or less, preferably 1 mol% or less, more preferably 0.50 mol% or less, and particularly preferably 0.3 mol% or less.

  The aliphatic polyester resin (A) provided in the present invention is sufficiently high molecular weight, excellent in melt tension, melted without using chain extenders such as isocyanate compounds and carbonate compounds, which are problematic in the environment. Since it is possible to provide a resin capable of finely adjusting the tension, it is particularly preferable that the aliphatic polyester resin (A) does not contain a structural unit derived from these chain extenders, but unless the effect of the present invention is significantly impaired, A structural unit derived from these chain extenders may be included. In addition, the unit derived from the chain extender may contain 1 type independently, and may contain 2 or more types by arbitrary ratios and combinations.

The amount thereof is usually 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol, based on a total amount of 100 mol% of all units constituting the aliphatic polyester resin (A). % Or less. However, when the aliphatic polyester resin (A) of the present invention is used as the biodegradable aliphatic polyester resin (A), which is also a feature of the aliphatic polyester resin (A), there is a diisocyanate and / or carbonate bond. , Since there is a possibility of inhibiting biodegradability, the amount used thereof is usually less than 1 mol%, preferably less than 1 mol%, based on the total amount of 100 mol% of all units constituting the aliphatic polyester resin (A), preferably 0.5 mol% or less, more preferably 0.1 mol% or less, and the urethane bond is usually less than 0.06 mol%, preferably 0.01 mol% or less, more preferably 0.001 mol% or less. is there.

  Specific examples of the carbonate compound include diphenyl carbonate dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and ethylene carbonate. In addition, carbonate compounds composed of the same or different hydroxy compounds derived from hydroxy compounds such as phenols and alcohols can be used.

Specifically, as the diisocyanate compound, 2,4-tolylene diisocyanate,
Known mixtures of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. And diisocyanate.

  Moreover, you may use a dioxazoline, a silicate ester, etc. as another chain extender. Specific examples of the silicate ester include tetramethoxysilane, dimethoxydiphenylsilane, dimethoxydimethylsilane, and diphenyldihydroxylane.

  Furthermore, from the viewpoint of increasing the melt tension, the aliphatic polyester resin (A) of the present invention may contain a unit derived from a peroxide having low toxicity. A peroxide may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.

  The aliphatic polyester resin (A) of the present invention usually has a carboxyl group and / or a hydroxyl group at its end. These carboxyl groups and / or hydroxyl groups may be sealed with a carbodiimide compound, an epoxy compound, a monofunctional alcohol, carboxylic acid, or the like. By sealing these carboxyl groups and / or hydroxyl groups, there is an advantage that the durability of the aliphatic polyester resin (A) can be improved.

  The carbodiimide compound is a compound having one or more carbodiimide groups in the molecule, and includes a monocarbodiimide compound having one carbodiimide group and a polycarbodiimide compound having two or more carbodiimide groups. A carbodiimide compound may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

  Specific examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, N. And '-di-2,6-diisopropylphenylcarbodiimide.

As the polycarbodiimide compound, the degree of polymerization (that is, the number of carbodiimide groups) is usually 4 or more, preferably 6 or more, and the upper limit is usually 40 or less, preferably 30 or less. Below the lower limit, odors and irritating odors may be caused. When the upper limit is exceeded, there may be poor dispersion when mixed with aliphatic polyester, and the hydrolysis inhibiting effect may not be obtained.

Specific examples of the polycarbodiimide compound include carbodilite HMV-8CA (manufactured by Nisshinbo), carbodilite LA-1 (manufactured by Nisshinbo), stabaxol P (manufactured by Rhein Chemie), starbactol P100 (manufactured by Rhein Chemie), and the like. Can be mentioned.
Particularly preferred is carbodilite which is an alicyclic polycarbodiimide. Specifically, HV-8CA and LA-1 are preferred in that they can maintain and improve workability, hydrolysis inhibiting effect, mechanical properties and the like. .

[1-4. Physical properties of aliphatic polyester (A)]
The physical properties of the aliphatic polyester (A) of the present invention are arbitrary as long as the effects of the present invention are not significantly impaired. However, it is preferable that the physical properties described below satisfy the ranges described below.

(Melting flow volume)
As an index representing the moldability of the aliphatic polyester resin (A), a melt flow volume (hereinafter referred to as “MVR” as appropriate), which is one of the melt indexes, can be used. The MVR in the aliphatic polyester resin (A) of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but the melt flow volume MVR per unit time measured at 190 ° C. and a load of 2.16 kg (2.16). ) has the value typically 0.050 cm ^3/10 minutes or more, preferably 0.10 cm ^3/10 minutes or more, more preferably 0.50 cm ^3/10 minutes or more, more preferably 1.0 cm ^3/10 minutes or more, even more preferably 1.5 cm ^3/10 minutes or more, particularly preferably 2.0c m ^3/10 minutes or more, and the upper limit thereof is generally 100 cm ^3/10 minutes or less, preferably 50 cm ^3/10 minutes or less, more preferably 25 cm ^3/10 minutes or less, more preferably 15cm ³ /
10 minutes or less, even more preferably 10 cm ^3/10 min, particularly preferably at most 6.0 cm ^3/10 min. When the MVR (2.16) is too small, the melt tension of the resin composition (A ′) becomes too high, the moldability becomes poor, the viscosity becomes high, and the resin composition (A ′) becomes gelled. If it is too large, the possibility of gelation becomes low, while the melt tension becomes too low, and the moldability may deteriorate.

Meanwhile, 190 ° C., the melt flow volume MVR (10.0) per unit of measurement with a load 10.0kg time also is optional unless significantly impairing the effects of the present invention, usually 5.0 cm ^3/10 minutes or more , preferably 10 cm ^3/10 minutes or more, more preferably 15cm ^3/10 minutes or more, more preferably 20 cm ^3/10 minutes or more, even more preferably 25 cm ^3/10 minutes or more, particularly preferably 30 cm ^3/10 minutes or more , and the upper limit thereof is generally 500 cm ^3/10 minutes or less, preferably 300 cm ^3/10 minutes or less, more preferably 100 cm ^3/10 minutes or less, more preferably 80 cm ^3/10 minutes or less, even more preferably 60cm ³ / 10 min, particularly preferably at most 50 cm ^3/10 min. If the MVR (2.16) is too small, the melt tension becomes too high, the moldability becomes poor, or the viscosity becomes high and the gelation of the resin composition (A ′) may be promoted. If it is too large, the possibility of gelation of the resin composition (A ′) becomes low, while the melt tension becomes too low, and the moldability may deteriorate.

Further, the value obtained by dividing the value of MVR (2.16) by the value of MVR (10.0) (hereinafter referred to as “MVR-R” as appropriate) is also used unless the effect of the present invention is significantly impaired. Although it is optional, it is usually 0.50 or more, preferably 1.0 or more, more preferably 5.0 or more, still more preferably 8.0 or more, still more preferably 10.0 or more, particularly preferably 10.5 or more. The upper limit is usually 25.0 or less, preferably 20.0 or less, more preferably 15.0 or less, still more preferably 12.0 or less, still more preferably 11.5 or less, and particularly preferably 11.
0 or less. When the value of MVR-R is too small, the possibility of gelation of the resin composition (A ′) decreases, while the melt tension becomes too low and the moldability may deteriorate. As a result of the melt elasticity, melt viscosity, etc. of the product (A ′) being increased, gelation of the resin composition (A ′) may be promoted.

  In addition, MVR can be measured according to the method of JIS-K7210, for example using the Takara Industries melt indexer. Specifically, by using the aliphatic polyester resin (A) dried at 80 ° C. for 12 hours for a melt indexer manufactured by Takara Industries, based on JIS-K7210, MVR (2.16) and MVR (10. 0) can be measured.

(Melt flow rate)
Also, a melt flow rate (hereinafter referred to as “MFR” as appropriate) can be used as an index. The MFR in the aliphatic polyester resin (A) of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but the MFR value under a condition of 190 ° C. and a load of 2.16 kg is usually 0.5 g / 10. Min, preferably 1.0 g / 10 min or more, more preferably 2.0 g / 10 min or more, and the upper limit is usually 100 g / 10 min or less, preferably 80 g / 10 min or less, more preferably 60 g / min. It is desirable that it is 10 minutes or less. When MFR is too small, when the aliphatic polyester resin (A) of the present invention is melted to obtain a resin composition (A ′), the viscosity of the resin composition (A ′) may become very high. Therefore, there is a possibility that a biodegradable laminated sheet cannot be stably obtained due to excessive load applied to the extruder when the molding process is performed or deterioration of the resin due to increased shearing heat generation. . If the MFR is too large, the viscosity of the molten resin may be significantly reduced. Therefore, since there is not sufficient melt tension at the time of sheet molding or secondary workability when the resin composition (A ′) is laminated on a base material to produce a biodegradable laminated sheet, a molding method, molding Depending on molding conditions such as temperature, there is a possibility that a biodegradable laminated sheet cannot be obtained.

  In addition, MFR can be measured based on JIS-K7210, for example. Moreover, as a measuring apparatus, it can measure on each condition, for example using the Takara Industries melt indexer.

(Amount of carboxyl group present at terminal of aliphatic polyester resin (A))
The amount of the carboxyl group present at the terminal of the aliphatic polyester resin (A) of the present invention (hereinafter referred to as “terminal carboxyl group” as appropriate) is arbitrary as long as the effects of the present invention are not significantly impaired. For the polyester resin (A), usually 0.1 μmol / g or more, preferably 1.0 μmol / g or more, more preferably 5.0 μmol / g or more, still more preferably 10.0 μmol / g or more, Particularly preferably 15.0 μmol / g or more, and the upper limit is usually 70 μmol / g or less, preferably 65 μmol / g or less, more preferably 60 μmol / g or less, still more preferably 40 μmol / g or less, Particularly preferably, it is 30 μmol / g or less. When there are too many amounts of a carboxyl group, the hydrolysis resistance of an aliphatic polyester resin (A) may worsen. The amount of the terminal carboxyl group can be measured, for example, by dissolving the aliphatic polyester resin (A) in benzyl alcohol and performing neutralization titration with a 0.1N sodium hydroxide aqueous solution. The measurement is performed a plurality of times, and the average value is preferably set as the amount of the terminal carboxyl group of the aliphatic polyester resin (A).

(Reduced viscosity)
The reduced viscosity η (η = η _sp / c) at 30 ° C. of the aliphatic polyester resin (A) of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1.6 dL / g or more, preferably Is 1.8 dL / g or more, more preferably 1.9 dL / g or more, still more preferably 2.0 dL / g or more, particularly preferably 2.1 dL / g or more, and the upper limit is usually 6 dL / g
g or less, preferably 5 dL / g or less, more preferably 4 dL / g or less, still more preferably 3 dL / g or less. When the reduced viscosity is too small, sufficient melt viscosity cannot be obtained at the time of sheet molding or secondary processability when the biodegradable laminated sheet is produced by laminating the resin composition (A ′) on the base material. If it is too large, the melt viscosity at the time of forming the sheet may become too high, or gelation may be promoted. The reduced viscosity can be measured using, for example, an Ubbelohde viscosity tube. Specifically, the aliphatic polyester resin (A) is dissolved in a phenol / tetrachloroethane (1: 1 weight ratio) solvent so as to be 0.5 g / dl, and the aliphatic polyester resin (A) solution at 30 ° C. The viscosity of the solution can be measured by measuring with a Ubbelohde viscosity tube.

(Amount of hydroxyl group present at terminal of aliphatic polyester resin (A))
The amount of the hydroxyl group present at the terminal of the aliphatic polyester resin (A) of the present invention (hereinafter referred to as “terminal hydroxyl group” as appropriate) is arbitrary as long as the effects of the present invention are not significantly impaired. With respect to the polyester resin (A), usually 10 μmol / g or more, preferably 15 μmol / g or more, more preferably 20 μmol / g or more, still more preferably 25 μmol / g or more, and the upper limit is usually 100 μmol / g. Mol / g or less, preferably 80 μmol / g or less, more preferably 70 μmol / g or less, even more preferably 60 μmol / g or less, even more preferably 50 μmol / g or less, and particularly preferably 40 μmol / g or less. is there. In addition, what is necessary is just to quantify the quantity of a terminal hydroxyl group using a suitable well-known analysis method. For example, when the terminal end of the aliphatic polyester resin (A) is a unit derived from 1,4-butanediol, and the terminal hydroxyl group of the unit is quantified, it is about 3.66 ppm using ¹ H-NMR. It can be quantified by the peak of the methylene proton on the carbon atom to which the terminal hydroxyl group that appears is directly bonded.

(Amount of vinyl group present at terminal of aliphatic polyester resin (A))
The amount of the vinyl group present at the terminal of the aliphatic polyester resin (A) of the present invention (hereinafter referred to as “terminal vinyl group” as appropriate) is arbitrary as long as the effects of the present invention are not significantly impaired. Usually 0.001 mol% or more, preferably 0.01 mol% or more, more preferably 0.025 mol% or more, still more preferably 0.04 mol% or more, particularly preferably 0, based on the polyester resin (A). 0.07 mol% or more, and its upper limit is usually 0.45 mol% or less, preferably 0.15 mol% or less, more preferably 0.1 mol% or less. When the amount of the terminal vinyl group is too small, the melt tension at the time of sheet molding or secondary workability when the biodegradable laminated sheet is produced by laminating the resin composition (A ′) on the base material is insufficient. In some cases, when the amount is too large, gelation of the resin composition (A ′) may be caused, resulting in poor appearance and adhesion due to gel of the obtained sheet laminate.

  The amount of the terminal vinyl group is, for example, a unit in which the main component of the aliphatic carboxylic acid unit (1) contained in the aliphatic polyester resin (A) is derived from succinic acid, or in the aliphatic polyester resin (A). When the main component of the derived aliphatic diol unit (2) is a unit derived from 1,4-butanediol, the aliphatic polyester resin (A) appearing near 5.15 ppm or near 5.78 ppm. It can be quantified by a proton peak on a carbon atom forming a double bond existing on the terminal side of the.

(YI value)
The degree of yellowing of the aliphatic polyester resin (A) of the present invention (hereinafter referred to as “YI value” as appropriate) is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually −2.0 or more, preferably Is -1.5 or more, more preferably -1.0 or more, still more preferably -0.5 or more, particularly preferably 0.0 or more, and the upper limit is usually 20.0 or less, preferably 15.0. Hereinafter, it is more preferably 10.0 or less, still more preferably 8.0 or less, particularly preferably 6.0 or less. When the YI value is too large, the yellowness of the aliphatic polyester resin (A) becomes strong and may cause coloring of the aliphatic polyester resin (A). The YI value can be measured based on the method of JIS K7105 using, for example, a colorimetric color difference meter Color Meter ZE2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

(Melting tension)
The melt tension F at 190 ° C. of the aliphatic polyester resin (A) of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.1 g or more, preferably 0.3 g or more, more preferably 0. The upper limit is usually 60 g or less, preferably 55 g or less, more preferably 50 g or less. When the melt tension F is too small, the melt tension of the resin composition (A ′) obtained by melt-kneading the aliphatic polyester resin (A) and the organic peroxide (B) is also small, so that the resin composition (A The molding processability of ') may not be improved, and if it is too large, the melt tension of the resin composition (A') becomes too large, so that the extensibility of the molten resin at the time of sheet molding is deteriorated. There is a possibility that mechanical properties such as body elongation will be significantly reduced. The melt tension F can be measured using, for example, a capillograph 1D manufactured by Toyo Seiki Seisakusho. Specifically, using a Toyo Seiki Seisakusho Capillograph 1D equipped with a nozzle having a diameter of 2.095 mm and a length of 8.1 mm, the molten aliphatic polyester resin (A) was extruded at a measurement temperature of 190 ° C. and the extrusion speed was 10 mm. The melted aliphatic polyester resin (A) strand extruded from the nozzle is wound with a roll through a pulley for detecting the tension, and the tension is measured.

(Melt viscosity)
The melt viscosity of the aliphatic polyester resin (A) of the present invention at 190 ° C. and a shear rate of 10 s ⁻¹ is usually 100 Pa · s or higher, preferably 150 Pa · s or higher, more preferably 200 Pa · s or higher, The upper limit is usually 15000 Pa · s or less, preferably 13000 Pa · s or less, more preferably 10,000 Pa · s or less. If the melt viscosity is too small, the melt viscosity of the resin composition (A ′) may be small and molding may be difficult. If it is too large, the melt viscosity of the resin composition (A ′) is too large. In some cases, the molded product cannot be obtained for reasons such as excessive load applied to the extruder during the molding process, and deterioration of the resin composition (A ′) due to increased shearing heat generation.

The melt viscosity of the aliphatic polyester resin (A) of the present invention at 190 ° C. and a shear rate of 1000 s ⁻¹ is usually 50 Pa · s or more, preferably 60 Pa · s or more, more preferably 70 Pa · s or more, Moreover, the upper limit is 1000 Pa * s or less normally, Preferably it is 800 Pa * s or less, More preferably, it is 600 Pa * s or less. If the melt viscosity is too small, the melt viscosity of the resin composition (A ′) may be small and molding may be difficult. If it is too large, the melt viscosity of the resin composition (A ′) is too large. In some cases, the molded product cannot be obtained for reasons such as excessive load applied to the extruder during the molding process, and deterioration of the resin composition (A ′) due to increased shearing heat generation.

In the aliphatic polyester resin of the present invention (A), 190 ° C., the molten viscosity at a shear rate of 1000 s ^-1, 190 ° C., the ratio ρ of the melt viscosity at a shear rate of 10s ^-1, typically 3.0 or more, preferably Is 3.2 or more, more preferably 3.5 or more. When ρ is too small, the reaction with the organic peroxide (B) may be difficult depending on the melt-kneading method.

  In addition, melt viscosity can be measured, for example using Toyo Seiki Seisakusho Capillograph 1D. Specifically, the melt viscosity can be measured at a measurement temperature of 190 ° C. using a Capillograph 1D manufactured by Toyo Seiki Seisakusho, which is provided with a nozzle having a diameter of 1 mm and a length of 20.6 mm.

(For gel)
The content of the gel component in the aliphatic polyester resin (A) of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 5% by weight or less, preferably 4% by weight or less, more preferably 3% by weight. % Or less. If the gel content is too much, the appearance of the biodegradable laminate sheet made of the resin composition (A ′) may be impaired, or the processability of the biodegradable laminate sheet may be poor and the molding speed may not be increased. is there. The gel content can be measured, for example, according to the following method. That is, first, 5 g of aliphatic polyester resin (A) is dissolved in 200 mL of chloroform and heated to reflux for 8 hours. Next, it is filtered using a filtration device having a 600 mesh comb, and the residue after filtration is dried under reduced pressure in an oven at 70 ° C. for 8 hours. The weight after drying is measured, and the gel content can be measured by the following formula.

Gel content = (X / 5) × 100
(However, X represents weight [g] after drying.)

(Melting point)
The melting point of the aliphatic polyester resin (A) of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and its upper limit. Is usually 160 ° C. or lower, preferably 150 ° C. or lower, more preferably 140 ° C. or lower. When the melting point is too low, when producing a biodegradable laminate sheet laminated on a substrate made of the resin composition (A ′), the release roll deteriorates and cannot be formed, or when the laminate sheet is used. In some cases, the resin layer of the laminated sheet is inferior in heat resistance such as deformation. On the other hand, when it is too high, when the biodegradable laminated sheet is secondarily processed, the heat seal expression temperature becomes high, and the molding process may be difficult.

[1-5. Method for producing aliphatic polyester resin (A)]
The aliphatic polyester resin (A) of the present invention can be produced by any known production method using any known catalyst as long as the aliphatic polyester resin (A) of the present invention is obtained. For example, it can be produced by melt polycondensation or solution heating dehydration condensation using an organic solvent. Especially, as a manufacturing method of the aliphatic polyester resin (A) of this invention, the melt polycondensation performed without a solvent from a viewpoint of economical efficiency and the simplicity of a manufacturing process is preferable.

  The aliphatic polyester resin (A) may be derived from biomass resources. There is no restriction | limiting in the kind of biomass resource, or its manufacturing method, unless the effect of this invention is impaired remarkably. For example, biomass resources obtained by induction to a carbon source through any known pretreatment / saccharification process such as chemical treatment of acids and alkalis, biological treatment using microorganisms, and physical treatment Can also be used.

  Hereinafter, the case where the aliphatic polyester resin (A) is produced by melt polycondensation will be described in detail, but the procedure of the melt polymerization method is not limited to this, and some steps may be omitted or replaced with others. You may change to a process or may have other arbitrary processes. The method for producing the aliphatic polyester resin (A) of the present invention is not limited to melt polycondensation.

  As the catalyst, a compound containing a group 1 to group 15 metal element excluding hydrogen and carbon in the periodic table is usually used. Specifically, for example, at least one or more selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium and potassium Compounds containing organic groups such as carboxylates, alkoxy salts, organic sulfonates or β-diketonates containing metals, and inorganic compounds such as oxides, composite oxides and halides of the above metals and their A mixture etc. are mentioned. In addition, a catalyst may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.

Among these, metal compounds containing titanium, zirconium, germanium, zinc, aluminum, magnesium and calcium, and mixtures thereof are preferable, and among these, titanium compounds, zirconium compounds and germanium compounds are particularly preferable. In addition, since the catalyst may have a high polymerization rate when it is melted or dissolved at the time of polymerization, a compound that is liquid at the time of polymerization or that is soluble in the ester low polymer and the aliphatic polyester resin (A) is preferred. Used in
Further, as a catalyst for producing the aliphatic polyester resin (A), for example, a catalyst prepared by previously mixing a titanium compound, an alkaline earth metal compound, and a phosphorus compound (hereinafter referred to as “metal composite catalyst” as appropriate). Can also be used.

  Content of titanium atom, alkaline earth metal atom and phosphorus atom in the catalyst is as follows: titanium atom content is T (molar basis), alkaline earth metal content is M (molar basis) and phosphorus atom content When the amount is P (molar basis), the lower limit of T / P (molar ratio) is usually 0.5 or more, preferably 0.7 or more, and the upper limit is usually 5.5 or less, more preferably 3 0.0 or less. If it is less than the lower limit, the catalytic activity tends to decrease. On the other hand, if the upper limit is exceeded, not only the coloration of the produced aliphatic polyester resin (A) will be remarkable, but the stability of the catalyst will be reduced, the catalyst will be deactivated, and further the catalyst deactivated substance will be in the product. May deteriorate the quality of the product.

  On the other hand, the lower limit of M / P (molar ratio) is usually 0.5 or more, preferably 0.7 or more, more preferably 0.9 or more, and the upper limit is usually 5.5 or less, preferably 3.0 or less. More preferably, it is 1.5 or less. If it is less than the lower limit value, the catalytic activity may decrease, and if it exceeds the upper limit value, the thermal stability of the aliphatic polyester resin (A) obtained using this catalyst may be deteriorated. In addition, alkaline earth metal may be deposited.

The catalyst is preferably produced by mixing an alcohol, a titanium compound, an alkaline earth metal compound, and an acidic phosphate compound and concentrating the mixture. More specifically, (i) a step of mixing, dissolving, and reacting an alcohol, a titanium compound, an alkali metal compound, and an acidic phosphate compound
(Ii) A step of concentrating by distilling off alcohol or the like from the reaction solution obtained in step (i) and further proceeding with the reaction to obtain a viscous liquid catalyst, a solid catalyst, or a mixture thereof. Preferably, it is manufactured by. At this time, it is considered that the alcohol used does not participate in the reaction but only serves as a solvent.

  The difference between the viscous liquid catalyst, the solid catalyst, or a mixture thereof and the resulting catalyst is due to the degree of concentration. The catalyst obtained in the step (ii) can be easily recovered as it is or after being dissolved in glycol such as ethylene glycol or 1,4-butanediol. In addition, what is distilled off at the time of concentration is alcohol, organic acid, etc. which are by-produced by reaction of alcohol, titanium compound, alkaline earth metal compound, and acidic phosphate compound used as a solvent.

The weight of the catalyst thus obtained is usually less than the total weight of the raw materials excluding the alcohol used as the solvent. The weight W ₁ of the resulting catalyst and the sum W ₀ of the weight of the titanium compound, alkaline earth metal compound, and acidic phosphate compound used in the mixing, that is, mixed with the alcohol in the step (i) above. The ratio W ₁ / W ₀ is usually 0.45 or more and usually 0.85
It is as follows. This ratio usually varies depending on the type of raw material compound used, the composition ratio, and the like.

(Solvent for dissolving catalyst)
In the method for producing the aliphatic polyester resin (A) of the present invention, the polycondensation reaction is preferably carried out in the absence of a solvent. Alternatively, a small amount of solvent may be used to dissolve the catalyst. Examples of the solvent for dissolving the catalyst include alcohols such as methanol, ethanol, isopropanol and butanol, diols such as ethylene glycol, butanediol and pentanediol, ethers such as diethyl ether and tetrahydrofuran, and nitriles such as acetonitrile. , Hydrocarbon compounds such as heptane and toluene, water and the like. As the solvent for dissolving the catalyst, one type may be used alone, or two or more types may be used in any ratio and combination.

  Further, the amount used is arbitrary as long as the aliphatic polyester resin (A) of the present invention is obtained, but it should be used so that the catalyst concentration is usually 0.0001% by weight or more and usually 99% by weight or less. Is desirable.

(amount to use)
When a metal material is used as the polymerization catalyst, the amount of catalyst used is usually 0.1 ppm or more, preferably 0.5 ppm or more, based on the weight of the aliphatic polyester resin (A) to be produced. More preferably 1 ppm or more, still more preferably 5 ppm or more, still more preferably 10 ppm or more, particularly preferably 20 ppm or more, and the upper limit is usually 30000 ppm or less, preferably 500 ppm or less, more preferably 250 ppm or less, still more preferably 100 ppm. In the following, it is desirable to use a catalyst amount that is particularly preferably 60 ppm or less. When the amount of the catalyst used is too small, the polymerization activity is lowered, and accordingly, the aliphatic polyester resin (A) is thermally decomposed during the production of the aliphatic polyester resin (A), and exhibits practically useful physical properties. The aliphatic polyester resin (A) may be difficult to obtain. If the amount is too large, it is not only economically disadvantageous, but the reason is not yet clear, but the concentration of terminal carboxyl groups in the aliphatic polyester resin (A) tends to increase, so the amount of terminal carboxyl groups In addition, the thermal stability and hydrolysis resistance of the aliphatic polyester resin (A) may decrease due to the increase in the residual catalyst concentration.

(Introduction time)
In addition, the mixing timing of the catalyst into the reaction system is not particularly limited as long as it is before the polycondensation reaction, and may be mixed in the reaction system at the time of charging the raw material. If the catalyst coexists in the situation where it is generated, the catalyst may be deactivated and the quality of the product may be deteriorated due to precipitation of foreign matters. Therefore, it is preferable to mix after the esterification reaction and / or transesterification reaction described below. There is a case.

(Manufacture of aliphatic polyester resin (A))
The method for producing the aliphatic polyester resin (A) of the present invention is arbitrary as long as the aliphatic polyester resin (A) of the present invention can be obtained, but it is usually melted using a known reactor and a known catalyst. It is preferable to produce by polycondensation.

(Reactor)
In the production method of the aliphatic polyester resin (A) of the present invention, a batch reaction and a continuous reaction are usually used. A batch reaction is usually a reaction in which an esterification reaction and / or a transesterification reaction and a polycondensation reaction are carried out batchwise, and a continuous reaction is usually an esterification reaction and / or a transesterification reaction and a polycondensation reaction. It is a method of performing continuously.

As a reaction apparatus for producing the aliphatic polyester resin (A) of the present invention batchwise, for example, a known vertical or horizontal stirred tank reactor can be used. For example, melt polymerization is performed in two stages of esterification and / or transesterification and reduced pressure polycondensation using the same or different reactors, and a vacuum pump and a reactor are used as the reduced pressure polycondensation reactor. A method of using a stirred tank reactor equipped with a evacuation pipe for decompression to be connected can be mentioned. Among them, a condenser is connected between the vacuum exhaust pipe connecting the vacuum pump and the reactor, and volatile components, unreacted monomers and the like generated during the condensation polymerization reaction in the condenser are included. The recovered method is preferably used.

  As a reaction apparatus for producing the aliphatic polyester resin (A) of the present invention continuously, an esterification and / or transesterification reaction tank and a polycondensation reaction tank are usually used. The esterification and / or transesterification reaction tank is not particularly limited. For example, a known vertical stirring complete mixing layer, vertical heat convection mixing layer, tower-type continuous reaction tank, or the like is used. Can do. Similarly, the polycondensation reaction tank is not particularly limited, and for example, a known vertical stirring polymerization tank, horizontal stirring polymerization tank, thin film evaporation polymerization tank, or the like can be used. In addition, the esterification and / or transesterification reaction tank and the polycondensation reaction tank may each be used alone or in any combination of two or more.

  As a production method of the aliphatic polyester resin (A), for example, after performing esterification reaction and / or transesterification reaction of the dicarboxylic acid component containing the aliphatic dicarboxylic acid and the aliphatic diol component, under reduced pressure, A method of increasing the degree of polymerization of the aliphatic polyester resin (A) while distilling off the diol produced by the transesterification of the terminal hydroxyl group of the aliphatic polyester resin (A), or the terminal carboxyl of the aliphatic polyester resin (A) Examples thereof include a method for increasing the degree of polymerization of the aliphatic polyester resin (A) while distilling off the dicarboxylic acid and / or its acid anhydride produced by the transesterification reaction of the group.

  As a method for producing the aliphatic polyester resin (A) of the present invention, the polymerization rate is high even at a lower temperature, and a high degree of polymerization of the aliphatic polyester resin (A) can be easily obtained without using a chain extender or the like. It may be preferable to use the latter method of distilling off the dicarboxylic acid and / or its acid anhydride. In this case, the removal of the dicarboxylic acid and / or its anhydride is usually carried out by distilling the dicarboxylic acid and / or its acid anhydride during the above polycondensation reaction. Since dicarboxylic acid tends to be an acid anhydride, it is often distilled by heating in the form of an acid anhydride. At this time, it may be desirable to remove both the chain or cyclic ether derived from the diol and / or the diol from the viewpoint of improving the polymerization rate.

  Here, when dicarboxylic acid and / or its acid anhydride and diol are distilled off, dicarboxylic acid and / or its anhydride contained in the total amount of dicarboxylic acid and / or anhydride and diol distilled off. The amount of is usually 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, from the viewpoint that an aliphatic polyester resin (A) having a high degree of polymerization can be produced. In particular, it is desirable that it is 90 mol% or more.

  As a condition of a production apparatus for producing an aliphatic polyester resin (A) having a high degree of polymerization by a method of distilling off dicarboxylic acid and / or acid anhydride thereof, a reaction vessel of an exhaust pipe for decompression connecting a vacuum pump and a reactor It is preferable to maintain the temperature of the side exhaust port at the lower of the melting point of the dicarboxylic acid anhydride or the boiling point of the dicarboxylic acid anhydride at the degree of vacuum during the polycondensation reaction. Thereby, the generated dicarboxylic acid and / or acid anhydride thereof can be efficiently removed from the reaction system, and the target aliphatic polyester resin (A) having a high degree of polymerization can be produced in a short time, which is preferable. Furthermore, it is more preferable to maintain the piping temperature from the reaction vessel side exhaust port to the condenser at the lower of the melting point of the acid anhydride or the boiling point in the degree of vacuum during the polycondensation reaction.

(material)
The raw material for producing the aliphatic polyester resin (A) of the present invention is arbitrary as long as the aliphatic polyester resin (A) of the present invention is obtained. However, it is preferable to use at least the components described in the above (Structural Unit) section as raw materials.

  Moreover, what is necessary is just to set as the usage-amount of a raw material so that the obtained aliphatic polyester resin (A) can have a desired structural unit in a desired ratio. Specifically, since the preferred range varies depending on the purpose of the aliphatic polyester resin (A), the type of raw material, etc., it cannot be generally stated, but the aliphatic diol component (2) relative to 1 mol of the aliphatic dicarboxylic acid component (1). Is usually 0.8 mol or more, preferably 0.9 mol or more, and the upper limit thereof is usually 3.0 mol or less, preferably 2.7 mol or less, particularly preferably 2.5 mol or less. It is desirable that

  On the other hand, when the polycondensation reaction is performed while distilling off the dicarboxylic acid and / or acid anhydride thereof when producing the aliphatic polyester resin (A) of the present invention, the purpose of the aliphatic polyester resin (A), Although the preferred range varies depending on the type of raw material and the like, it cannot be generally stated, but the amount of the aliphatic diol component (2) relative to 1 mol of the aliphatic dicarboxylic acid component (1) is usually 0.8 mol or more, preferably 0.8. It is 9 mol or more, more preferably 0.95 or more, and the upper limit is usually 1.15 mol or less, preferably 1.1 mol or less, particularly preferably 1.08 mol or less.

  In addition, when the aliphatic polyester resin (A) of the present invention contains an arbitrary unit, the corresponding component (monomer or oligomer; hereinafter referred to as “ "Optional component") may be used for the reaction. Arbitrary components may be used individually by 1 type, and 2 or more types may be used in arbitrary ratios and combinations.

  At this time, there is no limitation on the timing and method for introducing the above-mentioned optional components into the reaction system, and any method is possible as long as the effects of the present invention are not significantly impaired. For example, the timing and method of introducing the aliphatic hydroxycarboxylic acid component into the reaction system are not particularly limited as long as they are before the polycondensation reaction. For example, (1) a state in which the catalyst is previously dissolved in the aliphatic hydroxycarboxylic acid component solution And (2) a method of supplying the catalyst to the reaction apparatus at the same time as supplying the catalyst to the reaction apparatus.

(Additive)
Furthermore, when manufacturing the aliphatic polyester resin (A) of this invention, various additives can be used by arbitrary ratios and combinations as long as the effect of this invention is not impaired remarkably as needed. Examples of various additives include organic phosphorus compounds. Further, the amount used is arbitrary as long as the effects of the present invention are not significantly impaired. However, the content of the organophosphorus compound is usually the lower limit as the content of the phosphorus element in the aliphatic polyester resin (A). 0.01 ppm or more, preferably 0.1 ppm or more, more preferably 1 ppm or more, and particularly preferably 10 ppm or more. On the other hand, the upper limit is usually 5000 ppm or less, preferably 500 ppm or less, more preferably 300 ppm or less, still more preferably 100 ppm or less, and particularly preferably 30 ppm or less. If the amount used is too small, the thermal stabilization of the aliphatic polyester resin (A) may not be expressed. If the amount used is too large, the hydrolysis resistance of the produced aliphatic polyester resin (A) will be significantly reduced. There is. Various additives may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

  In order to contain the phosphorus element in the aliphatic polyester resin (A) of the present invention, a method in which the organic phosphorus compound shown below is mixed in any step during the production of the aliphatic polyester resin (A) is employed. From the viewpoint of ease of operation, a method of adding it at the time of charging the reaction is preferable.

  By mixing these phosphorus element-containing compounds at the time of production, the thermal stabilization of the aliphatic polyester resin (A) is expressed, and the production of the aliphatic polyester resin (A) at a higher temperature becomes possible.

The organophosphorus compound is preferably an organophosphorus compound selected from the group of organophosphate metal salts, phosphites and phosphonites, and mixtures thereof. Among these, phosphite and phosphonite are particularly preferred because the aliphatic polyester resin (A) has a high heat stabilizing effect during production and is excellent in durability such as hydrolysis resistance of the produced aliphatic polyester resin (A). Is more preferable, and phosphite is particularly preferable.
When the aliphatic polyester resin (A) of the present invention is produced, the order of mixing the organophosphorus compounds is not particularly limited. For example, the organic phosphorus compounds can be reacted together with the raw material monomers in a reactor. The aliphatic diol component and the aliphatic dicarboxylic acid component may be esterified or transesterified and then supplied to the reaction apparatus.

  Furthermore, in the present invention, when the aromatic dicarboxylic acid or an alkyl ester thereof is mixed and used as the dicarboxylic acid component in addition to the aliphatic carboxylic acid, the mixing order is not particularly limited. For example, as the first, The monomer can be put into the reactor in a batch and reacted. Second, after the diol component and the aliphatic dicarboxylic acid component are esterified or transesterified, the diol component and the aromatic dicarboxylic acid are reacted. Various methods such as a method of subjecting the components to an esterification reaction or a transesterification reaction and a polycondensation reaction can be employed.

(Reaction conditions)
The step of producing the aliphatic polyester resin (A) of the present invention by melt polycondensation is optional as long as the effects of the present invention are not significantly impaired. Usually, an esterification reaction and / or a transesterification reaction is performed, and the pressure is reduced. Then, a polycondensation reaction is performed.

(Reaction temperature, reaction atmosphere, reaction pressure, reaction time in esterification reaction and / or transesterification reaction)
Conditions such as reaction temperature, reaction atmosphere, reaction pressure, and reaction time in the esterification reaction and / or transesterification reaction are arbitrary as long as the effects of the present invention are not significantly impaired. However, the reaction temperature of the esterification reaction and / or transesterification reaction between the aliphatic dicarboxylic acid component and the aliphatic diol component is usually 150 ° C. or higher, preferably 180 ° C. or higher, and the upper limit is usually 260 ° C. or lower. Preferably it is 250 degrees C or less. The reaction atmosphere is usually preferably an inert gas atmosphere such as nitrogen or argon. Further, the reaction pressure is usually 10 kPa or more and usually ordinary pressure or less, and among them, ordinary pressure is preferable. The reaction time is usually 1 hour or more, and the upper limit is usually 10 hours or less, preferably 4 hours or less.

(Reaction temperature, reaction atmosphere, reaction pressure, reaction time in polycondensation reaction)
The reaction temperature of the polycondensation reaction is usually 150 ° C. or higher, preferably 180 ° C. or higher, and the upper limit is usually 280 ° C. or lower, preferably 260 ° C. or lower. If the reaction temperature is too low, the speed of the polycondensation reaction becomes extremely slow, and not only does it take a long time to produce the aliphatic polyester resin (A) with a high degree of polymerization, but also requires a high power stirrer, It may be economically disadvantageous. On the other hand, when the reaction temperature is too high, the polymerization rate is improved, but the aliphatic polyester resin (A) produced during the polycondensation reaction is simultaneously thermally decomposed to produce an aliphatic polyester resin (A) having a high degree of polymerization. Can be difficult. Therefore, in the method for producing the aliphatic polyester resin (A) of the present invention, control of the reaction temperature of the polycondensation reaction is extremely important.

  The reaction atmosphere is usually preferably an inert atmosphere such as nitrogen or argon.

The reaction pressure is usually 0.01 × 10 ³ Pa or more, preferably 0.01 × 10 ³ Pa or more, and the upper limit is usually 1.4 × 10 ³ Pa or less, preferably 0.4 × 10 ³ Pa or less. It is desirable to be under vacuum. If the pressure at the time of polymerization production is too high, the polycondensation time of the aliphatic polyester resin (A) becomes long, resulting in a decrease in molecular weight due to thermal decomposition of the aliphatic polyester resin (A), coloring of the aliphatic polyester resin (A), etc. It may be difficult to produce a resin composition (A ′) that is caused and exhibits practically sufficient characteristics. On the other hand, from the viewpoint of improving the polymerization rate, a polycondensation reaction using an ultra-high vacuum polymerization facility is preferred. However, if the pressure is too low, an extremely expensive facility investment may be required.

  The reaction time is usually 2 hours or more, and the upper limit is usually 15 hours or less, preferably 8 hours or less, more preferably 6 hours or less. If the reaction time is too short, the reaction becomes insufficient, and the degree of polymerization of the aliphatic polyester resin (A) may be lowered. Further, since the tensile elongation at break of the aliphatic polyester resin (A) is low and the amount of terminal carboxyl groups is large, there is a possibility that the deterioration of the tensile elongation at break is significant. On the other hand, when the reaction time is too long, the molecular weight is decreased due to thermal decomposition of the aliphatic polyester resin (A), and not only the tensile elongation at break is decreased, but also the durability of the aliphatic polyester resin (A) is affected. The terminal carboxyl group to give may increase by thermal decomposition. Moreover, gelatinization of the aliphatic polyester resin (A) obtained may be caused.

(Average pressure reduction and average pressure increase in polycondensation reaction)
When the polycondensation reaction proceeds, the pressure of the reaction system is usually reduced to the above reaction pressure, and it is preferable to reduce the pressure while controlling the average pressure reduction rate. As a specific average pressure reduction rate, the average pressure reduction from normal pressure to 2 hPa is usually 2 hPa / min or more, preferably 3 hPa / min or more, more preferably 4 hPa / min or more, still more preferably 5 hPa / min or more, particularly preferably. Is 6 hPa / min or more, and the upper limit is usually less than 15 hPa / min, preferably 12 hPa / min or less, more preferably 10 hPa / min or less, further preferably 9 hPa / min or less, and particularly preferably 8 hPa / min or less. It is desirable. If the average pressure reduction rate is too slow, the polycondensation time may be prolonged. On the other hand, if it is too fast, the amount of evaporation of the volatile components in the reaction apparatus increases, the amount of heat of evaporation taken away from the polymer increases, and the polymer temperature may decrease too much.

[2. Organic peroxide (B)]
The resin composition (A ′) of the present invention is obtained by melt-kneading the aliphatic polyester resin (A) of the present invention and the organic peroxide (B). Any organic peroxide (B) can be used in any ratio as long as the effects of the present invention are not significantly impaired. Among them, as the organic peroxide (B), at least one selected from the group consisting of ketone peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, and hydroperoxide. It is preferable to use a compound. More preferably,
Peroxyesters, peroxyketals, and dialkyl peroxides, and more preferably, dialkyl peroxides have an appropriate half-life temperature that facilitates operation, hydrogen abstraction ability, and are less odorous. This is effective in controlling the structure.
In addition, an organic peroxide (B) may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations. Below, the description of a specific preferable compound is enumerated.

  Specific examples of the ketone peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, and acetylacetone peroxide.

  Specific examples of the diacyl peroxide include diisobutyryl peroxide, di3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide and the like.

  Specific examples of peroxydicarbonate include diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate. Etc.

  Specific examples of peroxyesters include t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxy-2-ethylhexanoate. And t-butylperoxy-2-ethylhexanoate.

  Specific examples of peroxyketal include 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methylcyclohexane, n-butyl 4,4-di- (T-butylperoxy) valerate and the like.

  Specific examples of the dialkyl peroxide include dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, 2.5-dimethyl-2,5-di (t- Butylperoxy) hexane, di (2-t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene-3, and the like.

  Specific examples of the hydroperoxide include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, and the like.

  The amount of the organic peroxide (B) used is usually 0.0001 parts by weight or more, preferably 0.0005 parts by weight or more, more preferably 0.000 parts by weight or more with respect to 100 parts by weight of the aliphatic polyester resin (A). The upper limit is usually not more than 0.06 parts by weight, preferably not more than 0.03 parts by weight, more preferably not more than 0.01 parts by weight. When the amount of the organic peroxide (B) is too small, the crosslinking effect may not be obtained. When the amount is too large, the organic peroxide (B) unreacted with the resin composition (A ′) of the present invention, Residues may remain. In addition, when the amount of the organic peroxide (B) used is in the above range, the resin composition (A ′) of the present invention is microcrosslinked in a desired amount, so that the melt tension and the like are efficiently improved. The advantage that not only the moldability is increased but also the odor is not generated.

  In addition, unless the effect of the present invention is significantly impaired, the organic peroxide (B) is mixed with the aliphatic polyester resin (A) in a range exceeding the upper limit of the amount of the organic peroxide (B) used, The resin composition (A ′) is produced, and then mixed with the aliphatic polyester resin (A) and diluted, so that the amount of the organic peroxide (B) used is within the mixing range (A It is also possible to manufacture ').

[2-1. Physical properties of resin composition (A ′)]
The physical properties of the resin composition (A ′) of the present invention are arbitrary as long as the effects of the present invention are not significantly impaired. However, it is preferable that the physical properties described below satisfy the ranges described below.

(Amount of aliphatic dicarboxylic acid unit (1) contained)
The amount of the aliphatic dicarboxylic acid unit (1) contained in the resin composition (A ′) of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually contained in the aliphatic polyester resin (A). This is the same as the amount of the aliphatic dicarboxylic acid unit (1).

  In addition, the amount of the aliphatic dicarboxylic acid unit (1) contained in the resin composition (A ′) is, for example, the aliphatic dicarboxylic acid represented by (formula (1) described in the section of (constituent unit). Acid unit).

(Amount of aliphatic diol unit (2) contained)
The amount of the aliphatic diol unit (2) contained in the resin composition (A ′) of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually contained in the aliphatic polyester resin (A). The amount is the same as the amount of the aliphatic diol acid unit (2).

In addition, the amount of the aliphatic diol unit (2) contained in the resin composition (A ′) is, for example, the aliphatic diol unit represented by (formula (2) described in the above (Constitutional unit) section. ) In accordance with the method described in (1).

(Amount of aliphatic hydroxycarboxylic acid units (3) and (4) contained)
The amount of the aliphatic hydroxycarboxylic acid units (3) and (4) contained in the resin composition (A ′) of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired. This is the same as the amount of the aliphatic hydroxycarboxylic acid units (3) and (4) contained in the polyester resin (A).

  In addition, the amount of the aliphatic hydroxycarboxylic acid units (3) and (4) contained in the resin composition (A ′) is represented by, for example, (formula (3) described in the section of (constituent unit). The aliphatic hydroxycarboxylic acid unit represented by formula (4) and the aliphatic hydroxycarboxylic acid unit represented by formula (4) can be measured.

(Amount of unsaturated aliphatic dicarboxylic acid unit (5), (6), (7) contained)
Unsaturated aliphatic dicarboxylic acid units (5), (6) and (7) contained in the resin composition (A ′) of the present invention (hereinafter collectively referred to as “aliphatic unsaturated dicarboxylic acid units”) When the aliphatic polyester resin (A) and the organic peroxide (B) are melt-kneaded, the double bond in the reaction usually reacts with the organic peroxide (B) and is contained in the aliphatic bond. Since the polyester resins (A) are cross-linked, part or all of them become single bonds. Therefore, the degree of crosslinking between the aliphatic polyester resins (A) can be measured by measuring the amount of the aliphatic unsaturated dicarboxylic acid unit contained in the resin composition (A ′) of the present invention.

  The proportion of the aliphatic unsaturated dicarboxylic acid units contained in the resin composition (A ′) of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but all units contained in the resin composition (A ′) Is usually 0.25 mol% or less, preferably 0.18 mol% or less, more preferably 0.058 mol% or less, still more preferably 0.048 mol% or less, particularly preferably 0.038 mol%. % Or less. When the ratio is too large, when the resin composition (A ′) is molded, branch chains are likely to be generated excessively, and the molding process may be difficult.

  In addition, the amount of the aliphatic unsaturated dicarboxylic acid unit contained in the resin composition (A ′) is, for example, the aliphatic unsaturation represented by (formula (5)) described in the section of (constituent unit) described above. It can be measured according to the method described in (dicarboxylic acid unit).

(Amount of vinyl group present at terminal of resin composition (A ′))
The amount of the terminal vinyl group of the resin composition (A ′) of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but the terminal vinyl group of the aliphatic polyester resin (A) and the organic peroxide (B In general, it is less than the amount of the terminal vinyl group of the aliphatic polyester resin (A). In addition, the quantity of a terminal vinyl group can be measured similarly to the case of the vinyl group contained in aliphatic polyester resin (A), for example.

(Amount of carboxyl group present at terminal of resin composition (A ′))
The amount of the terminal carboxyl group of the resin composition (A ′) of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 70 μmol / g or less with respect to the resin composition (A ′), Preferably it is 65 μmol / g or less, more preferably 60 μmol / g or less, still more preferably 40 μmol / g or less, particularly preferably 30 μmol / g or less, and its lower limit is usually 0.1 μmol / g or more. Preferably, it is 1.0 μmol / g or more, more preferably 5.0 μmol / g or more, still more preferably 10.0 μmol / g or more, and particularly preferably 15.0 μmol / g or more. When there is too much quantity of a terminal carboxyl group, the hydrolysis resistance of a resin composition (A ') may worsen. In addition, the quantity of a terminal carboxyl group can be measured similarly to the case of the carboxyl group contained in aliphatic polyester resin (A), for example.

(Reduced viscosity)
The reduced viscosity η ′ (η ′ = η _sp ′ / c) at 30 ° C. of the resin composition (A ′) of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1.6 dL / g. Or more, preferably 1.8 dL / g or more, more preferably 1.9 dL / g or more, still more preferably 2.0 dL / g or more, particularly preferably 2.1 dL / g or more, and the upper limit is usually 6 dL / G or less, preferably 5 dL / g or less, more preferably 4 dL / g or less, still more preferably 3 dL / g or less. If the reduced viscosity is too small, a sufficient melt viscosity may not be obtained when the resin composition (A ′) is molded. If it is too large, the melt viscosity will be increased when the resin composition (A ′) is molded. It may be too much or promote gelation. In addition, a reduced viscosity can be measured by the method similar to the case of an aliphatic polyester resin (A), for example.

(Melting tension)
The melt tension F ′ at 190 ° C. of the resin composition (A ′) of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 2.0 g or more, preferably 2.5 g or more, more preferably The upper limit is usually 60 g or less, preferably 55 g or less, more preferably 50 g or less. If the melt tension is too small, the effect of improving the molding processability of the resin composition (A ′), which is the effect of the present invention, may not be obtained. The mechanical properties such as elongation of a molded article such as a film may be deteriorated. In addition, melt tension can be measured similarly to the melt tension of aliphatic polyester resin (A), for example.

(Melt viscosity)
In the resin composition (A ′) of the present invention, the melt viscosity at a temperature of 190 ° C. and a shear rate of 10 s ⁻¹ is not particularly limited, but is usually 100 Pa · s or more, preferably 150 Pa · s or more, more preferably 200 Pa · s. The upper limit is usually 15000 Pa · s or less, preferably 13000 Pa · s or less, more preferably 10000 Pa · s or less.

In the resin composition (A ′) of the present invention, the melt viscosity at a temperature of 190 ° C. and a shear rate of 1000 s ⁻¹ is usually 50 Pa · s or more, preferably 60 Pa · s or more, more preferably 70 Pa · s or more. The upper limit is usually 1000 Pa · s or less, preferably 800 Pa · s or less, more preferably 600 Pa · s or less.

In the resin composition of the present invention (A '), the temperature 190 ° C., the molten viscosity at a shear rate of 1000 s ^-1, a temperature 190 ° C., the ratio ρ'of melt viscosity at a shear rate of 10s ^-1 is usually 3.0 As mentioned above, Preferably it is 3.2 or more, More preferably, it is 3.5 or more. When ρ ′ is too small, it may be difficult to mold the resin composition (A ′) depending on the molding method to be applied and molding conditions.

  In addition, melt viscosity can be measured similarly to the case of aliphatic polyester resin (A), for example.

(Melting point)
The melting point of the resin composition (A ′) of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually the same as the melting point of the aliphatic polyester resin (A). When the melting point is too low, the heat resistance of the molded product may be a problem, and when it is too high, the molding process of the resin composition (A ′) may be difficult.

[2-2. Preferred Relationship of Physical Properties in Aliphatic Polyester Resin (A) and Resin Composition (A ′)]
(Content of each structural unit)

  Furthermore, the ratio of the total of aliphatic hydroxycarboxylic acid units (3) and aliphatic hydroxycarboxylic acid units (4) to the total of aliphatic unsaturated dicarboxylic acid units contained in the resin composition (A ′) of the present invention. y is arbitrary as long as the effects of the present invention are not significantly impaired. However, the double bond in the aliphatic unsaturated dicarboxylic acid unit contained in the aliphatic polyester resin (A) usually reacts with the organic peroxide (B), and all / or part thereof is a single bond. Therefore, usually, the amount of the aliphatic unsaturated dicarboxylic acid unit contained in the resin composition (A ′) is smaller than the amount of the aliphatic unsaturated dicarboxylic acid unit contained in the aliphatic polyester resin (A). Therefore, the value of y is usually determined based on the aliphatic hydroxycarboxylic acid unit (3) and aliphatic hydroxycarboxylic acid unit (with respect to the total of unsaturated aliphatic dicarboxylic acid units contained in the aliphatic polyester resin (A) of the present invention ( It becomes larger than the value of the total ratio x in 4).

  Specifically, the value obtained by dividing y by x (y / x) is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1.05 or more, preferably 1.07 or more, more preferably 1 .10 or more, and usually less than 5.00, preferably 4.95 or less, more preferably 4.90 or less. When the value of y / x is too small, the crosslinking in the resin composition (A ′) is difficult to develop, and thus the effect of improving the molding processability of the resin composition (A ′), which is the effect of the present invention, cannot be obtained. If it is too large, the crosslinking in the resin composition (A ′) will develop too much, which makes it difficult to mold the resin composition (A ′). There is a possibility of too much.

Moreover, when the aliphatic polyester resin (A) and the organic peroxide (B) are melt-kneaded, the crosslinking between the aliphatic polyester resins (A) usually proceeds, the molecular weight increases, and the reduced viscosity increases. Accordingly, the value (η ′ / η) obtained by dividing the reduced viscosity η ′ at 30 ° C. described in the above (reduced viscosity) by the reduced viscosity η at 30 ° C. described in the above (reduced viscosity) is Although it is optional as long as the effect is not significantly impaired, it is usually 1.05 or more, preferably 1.10 or more, more preferably 1.20 or more, and the upper limit is usually 1.80 or less, preferably 1. It is 75 or less, more preferably 1.70 or less.
If η ′ / η is too small, the crosslinking is not developed, so the melt tension of the resin composition (A ′) is insufficient, sticking to the cooling roll during extrusion lamination sheet molding, or uneven thickness in inflation molding There is a possibility of becoming. On the other hand, if η ′ / η is too large, cross-linking develops too much and the gel content may become very large. Accordingly, in the molding process, the flow of the resin composition (A ′) becomes unstable, or the gel content can be visually confirmed on the surface of the molded body, making it difficult to obtain a molded body with a beautiful appearance. There is a possibility.

Further, when the aliphatic polyester resin (A) and the organic peroxide (B) are melt-kneaded, the aliphatic polyester resin (A) is usually cross-linked to increase the molecular weight, and the aliphatic polyester resin. Since branching develops in (A), the melt tension of the resin composition (A ′) increases. Accordingly, the value (F ′ / F) obtained by dividing the melt tension F ′ described in the (melt tension) by the melt tension F described in the (melt tension) described above (F ′ / F) does not significantly impair the effects of the present invention. Although it is optional, it is usually 1.5 or more, preferably 1.55 or more, more preferably 1.60 or more, and the upper limit is usually 20 or less, preferably 19 or less, more preferably 18 or less. .
When F ′ / F is too small, the molecular weight and the branching development in the aliphatic polyester resin (A) are insufficient, so that the melt tension of the resin composition (A ′) may not be improved. is there. In addition, when F ′ / F is too large, cross-linking develops excessively, so that aggregates are conspicuous on the surface of the resin composition (A ′), the extensibility at the time of sheet molding decreases, and the elongation of a molded body such as a film. There is a possibility that the mechanical properties such as

When the aliphatic polyester resin (A) and the organic peroxide (B) are melt-kneaded, the crosslinking between the aliphatic polyester resins (A) proceeds, the molecular weight increases, and the aliphatic polyester resin (A) Therefore, the non-Newtonian property increases in the low shear rate region of the resin composition (A ′), that is, the melt viscosity does not take a constant value with respect to the shear rate, and the melt viscosity increases. Therefore, the value (ρ ′ / ρ) obtained by dividing the melt viscosity ρ ′ described in the above (melt viscosity) by the melt viscosity ρ described in the above (melt viscosity) (ρ ′ / ρ) does not significantly impair the effects of the present invention. Although it is optional, it is usually 1.1 or more, preferably 1.15 or more, more preferably 1.20 or more, and the upper limit is usually 3.0 or less, preferably 2.9 or less, more preferably 2.8 or less.
When ρ ′ / ρ is too small, the molecular weight and the branching of the aliphatic polyester resin (A) are not sufficiently developed, and the moldability may not be sufficiently improved. In addition, when ρ ′ / ρ is too large, since the crosslinking has developed too much, the gel content that is a solvent-insoluble component may be very large.

(For gel)
The gel content in the resin composition (A ′) of the present invention is usually less than 10% by weight, preferably 8% by weight or less, more preferably 6% by weight or less. When the gel content is too large, aggregates are scattered on the surface of a molded article such as a film, and the molded article does not have an excellent appearance, and the aggregate may adversely affect the mechanical properties of the molded article. In addition, a gel part can be measured similarly to the case of an aliphatic polyester resin (A), for example.

[2-3. Production Method of Resin Composition (A ′) of the Present Invention]
The resin composition (A ′) of the present invention is obtained by melt-kneading the aliphatic polyester resin (A) of the present invention and the organic peroxide (B).

(Method of kneading)
Kneading can be carried out using any apparatus and under any conditions and under any conditions as long as the effects of the present invention are not significantly impaired. As a kneading apparatus, for example, a batch-type kneader such as a roll or an internal mixer, a one-stage type, a two-stage type continuous kneader, a twin-screw extruder, a single-screw extruder, or the like can be used. . Among these, a twin screw extruder and a single screw extruder are preferable. Examples of the kneading method include a method of mixing various additives in a place where the mixture is melted by heating. In addition, blending oils and the like can be used for the purpose of uniformly dispersing various additives. One type of kneading apparatus may be used alone, or two or more types may be used in any combination. Moreover, the kneading | mixing method may be performed individually by 1 type, and may be performed combining 2 or more types arbitrarily.

(temperature)
The kneading temperature is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 80 ° C. or higher, preferably 85 ° C. or higher, more preferably 90 ° C. or higher, and the upper limit is usually 260 ° C. or lower, preferably It is 250 ° C. or lower, more preferably 240 ° C. or lower. If the temperature is too low, the aliphatic polyester resin (A) may not be sufficiently melted and mixing may be difficult, or the crosslinking reaction may not proceed sufficiently. When the temperature is too high, the aliphatic polyester resin (A) may be thermally decomposed to lower the molecular weight, or the crosslinking reaction may proceed too much to generate a large amount of gel component.

(Kneading time)
The kneading time cannot be generally specified depending on the kind of the kneading apparatus, the kind of the aliphatic polyester resin (A) and the organic peroxide (B), but is usually 0.1 minutes or more and usually 20 minutes or less.

(Various additives)
The resin composition (A ′) of the present invention can contain various additives as long as the effects of the present invention are not significantly impaired. In addition, the order, method, addition amount, and the like of mixing various additives into the resin composition (A ′) of the present invention include various additives contained in the final resin composition (A ′). As long as the effect of is not significantly impaired, it can be arbitrarily determined. Various additives, aliphatic polyester resin (A) and organic peroxide (B) may be mixed and then kneaded, or aliphatic polyester resin (A) and organic peroxide (B) may be kneaded. However, various additives may be mixed.

  Various additives can be used as long as the effects of the present invention are not significantly impaired. For example, heat stabilizers such as crystal nucleating agents, fillers, antioxidants, ultraviolet absorbers, light stabilizers (light-proofing agents), antistatic agents, lubricants, antiblocking agents, mold release agents, antifogging agents, crystal nucleating agents , Plasticizers, colorants, fillers, compatibilizers, flame retardants, surface wetting improvers, dispersion aids, various surfactants, and the like. Among these, it is preferable to use a crystal nucleating agent and a filler. In addition, an additive may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.

  Specific examples of the crystal nucleating agent include inorganic nucleating agents and organic nucleating agents. In addition, a crystal nucleating agent may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

  Specific examples of inorganic nucleating agents include talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, and barium sulfate. And metal salts such as aluminum oxide, neodymium oxide, and phenylphosphonate. In addition, these inorganic nucleating agents may be modified with an organic substance in order to improve dispersibility in the resin composition (A ′).

  On the other hand, specific examples of the organic nucleating agent include fatty acid metal salts such as calcium stearate, fatty acid amides such as stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxystearic acid amide, and erucic acid amide; polyolefin And wax.

  A conventionally well-known filler can be used as a filler. Fillers are generally roughly classified into inorganic fillers and organic fillers.

Specific examples of inorganic fillers include anhydrous silica, mica, talc, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon , Wollastonite, calcined pearlite, silicates such as calcium silicate and sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate and calcium hydroxide, ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, barium sulfate, etc. And the like.
In addition, when the resin composition (A ′) of the present invention is formed into a sheet, in particular, it is possible to improve the roll-off property or to improve the secondary workability such as punching workability of the sheet laminate with a cutter blade or the like. From the viewpoint, the resin composition (A ′) preferably contains an inorganic filler. In this case, the content of the inorganic filler in the resin composition (A ′) is usually relative to the total amount of the aliphatic polyester resin (A) and the inorganic filler contained in the resin composition (A ′). 0.01 wt% or more, preferably 0.02 wt% or more, more preferably 0.05 wt% or more, and the upper limit is usually 70 wt% or less, preferably 50 wt% or less, more preferably 10 wt% % Or less is desirable.
If the amount of inorganic filler is too small, there is a possibility that the roll-off improvement effect and punching performance may not be improved. Since work becomes frequent, workability deteriorates, which is not preferable.

  Specific examples of the organic filler include raw starch, processed starch, pulp, chitin / chitosan, coconut shell powder, wood powder, bamboo powder, bark powder, kenaf, and cocoon powder. The content of the organic filler in the resin composition (A ′) of the present invention is usually 0.01% by weight or more and usually 70% by weight or less.

  The timing of mixing these additives may be added, for example, when the raw material is charged in the former step or may be added when the raw material is charged in the subsequent step, and any method for producing the resin composition (A ′) of the present invention. You may mix in a process.

  The resin composition (A ′) of the present invention may contain any other material in addition to the above additives. In addition, other arbitrary materials may be used individually by 1 type, and may use 2 or more types by arbitrary ratios and combinations. As other arbitrary materials, the material described below is mentioned, for example. In addition, the additive illustrated below is a specific example of an additive, and as an additive, it is not limited to the content as described in the following.

(Other aliphatic polyester resins)
The resin composition (A ′) of the present invention may contain a biodegradable resin other than the aliphatic polyester resin (A) of the present invention. Examples of the biodegradable resin include aliphatic polyester resins, aliphatic hydroxycarboxylic acid resins, polysaccharides, aliphatic-aromatic copolymer polyesters, and other degradable resins. Of these, aliphatic polyester resins are preferable, and various conventionally known resins can also be used. Among these, the aliphatic polyester resin is preferably a biodegradable polymer or a thermoplastic resin. In addition, an aliphatic polyester-type resin may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

As the aliphatic polyester-based resin, one having an aliphatic and / or alicyclic diol unit as a main constituent unit is usually preferable, and an aliphatic and / or alicyclic dicarboxylic acid unit and other common units as required. It may be composed of polymerized units.
Examples of the polysaccharide include modified cellulose such as cellulose and cellulose acetate, chitin, chitosan, starch, and modified starch. Other degradable resins include polyalkylene glycols such as polyvinyl alcohol, modified polyvinyl alcohol, polyethylene glycol, and polypropylene glycol. In addition, a polysaccharide may be used individually by 1 type and may use 2 or more types by arbitrary ratios and combinations. Other degradable resins may be used alone, or two or more may be used in any ratio and combination.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polyolefin, polyvinylidene fluoride, and the like. Halogen-containing resin, polystyrene, styrene resin such as acrylonitrile-butadiene-styrene copolymer, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyisoprene, polybutadiene, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer Polymeric rubber, elastomers such as styrene-isoprene copolymer rubber, polyamide resins such as nylon 6,6, nylon 6, etc., polyvinyl acetate, methacrylate resins, polycarbonate Resin, polyacetal, polyphenylene oxide, polyurethane, and the like. In addition, a thermoplastic resin may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.
When the resin composition (A ′) of the present invention contains the aliphatic polyester resin (A) of the present invention and the above resin, the aliphatic polyester of the present invention contained in the resin composition (A ′) of the present invention. The amount of the resin (A) is usually 0.1% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and its upper limit is usually 99.9% by weight or less, preferably 85% by weight. Hereinafter, it is desirable that the content is 60% by weight or less.

(Compatibilizer)
In order to improve the compatibility of the resin composition (A ′), the resin composition (A ′) of the present invention may contain a compatibilizing agent.

Any compatibilizer can be used as long as the effects of the present invention are not significantly impaired. Specific examples of the compatibilizer include an ester group, a carboxylic acid anhydride, an amide group, an ether group, a cyano group, an unsaturated hydrocarbon group, an epoxy group, an acrylic group at the terminal or main chain of the aliphatic polyester resin (A). And a compound to which a group, a methacryl group, an aromatic hydrocarbon group or the like is added.
One type of compatibilizer may be used alone, or two or more types may be used in any combination and ratio. In particular, when the resin composition (A ′) of the present invention contains a resin other than the aliphatic polyester of the present invention, the resin composition (A ′) of the present invention preferably contains a compatibilizing agent.

  The amount of the compatibilizer used is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 0.01 parts by weight or more, preferably 0.1 parts by weight with respect to the resin composition (A ′) of the present invention. Part or more, more preferably 1 part by weight or more, and usually 50 parts by weight or less, preferably 30 parts by weight or less, more preferably 10 parts by weight or less. Moreover, when there is too little usage-amount, the effect of a compatibilizing agent may become small, and when too large, manufacturing cost may become high. In addition, when using 2 or more types of compatibilizers together, it is preferable that the sum total of those usage amount satisfy | fills the said range.

  Further, the compatibilizing agent may be mixed in any process for producing the resin composition (A ′) of the present invention.

(Other additives)
The resin composition (A ′) of the present invention may further contain additives exemplified below in addition to the above materials. The content of the additive is not limited as long as the effect of the present invention is not impaired, but the total content of the additive to be mixed is usually 0.01% by weight or more with respect to the resin composition (A ′) of the present invention. Usually, it is desirable that it is 10 wt% or less. Moreover, an additive can be mixed with the resin composition (A ') of this invention with arbitrary forms. For example, they may be mixed in a solid state, mixed as a solution dissolved in a solvent, or mixed as a slurry dispersed in a solvent. In addition, the additive illustrated below is a specific example of an additive, and as an additive, it is not limited to the content as described in the following.

(Heat stabilizer)
The resin composition (A ′) of the present invention may contain a heat stabilizer. Thereby, the advantage of suppressing deterioration of resin at the time of sheet forming can be obtained.

  Any thermal stabilizer can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert. -Butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol is general-purpose and is preferably used from the viewpoint of maintaining hue (YI).

  Further, the content of the heat stabilizer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 100 ppm or more, preferably 200 ppm or more, based on the resin composition (A ′) of the present invention. The upper limit is usually 5 parts by weight or less, preferably 1 part by weight or less, more preferably 0.5 parts by weight or less. When the content is too small, the effect of the heat stabilizer is reduced, and as a result of the remarkable development of the branched structure at the time of forming the sheet, there is a possibility of generating irregularities. Moreover, when there is too much content, manufacturing cost may become high and bleeding out of a heat stabilizer may arise. In addition, when using 2 or more types of heat stabilizers together, a synergistic effect can also be anticipated, the effect may be improved remarkably, and it is used suitably. It is preferable that the sum of the amounts used satisfies the above range. In the present specification, “ppm” represents a ratio based on weight.

  The heat stabilizer may be mixed in any process for producing the resin composition (A ′) of the present invention.

(Light proofing agent)
The resin composition (A ′) of the present invention may contain a light proofing agent. Thereby, the advantage that deterioration (namely, fall of molecular weight) of the resin composition (A ') by light can be suppressed is acquired.

  Any light-proofing agent can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include hindered amine stabilizers. A light stabilizer may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. In particular, it is preferable to use different types of light-proofing agents in combination, and it is preferable to use them in combination with an ultraviolet absorber. Among them, it is preferable to use a combination of a hindered amine light stabilizer and an ultraviolet absorber.

  The content of the light stabilizer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 100 ppm or more, preferably 200 ppm or more, and its upper limit with respect to the resin composition (A ′) of the present invention. Is usually 5 parts by weight or less, preferably 1 part by weight or less, more preferably 0.5 parts by weight or less. When there is too little content, the effect of a light-resistant agent may become small. Moreover, when there is too much content, manufacturing cost may become high, the heat resistance of a resin composition (A '), a moldability may be inferior, and the bleedout of a light-resistant agent may arise. . In addition, when using 2 or more types of light resistance agents together, it is preferable that the total of those usage amount satisfy | fills the said range.

The light stabilizer may be mixed in any process for producing the resin composition (A ′) of the present invention.

(UV absorber)
The resin composition (A ′) of the present invention may contain an ultraviolet absorber.

  Any ultraviolet absorber can be used as long as the effects of the present invention are not significantly impaired. Specific examples thereof include 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol, 2- (4,6-diphenyl-1,3,5). -Triazin-2-yl) -5-[(hexyl) oxy] phenol and the like. A ultraviolet absorber may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. In particular, it is preferable to use a combination of different types of ultraviolet absorbers, and it is also preferable to use them in combination with a light-resistant agent.

  Further, the content of the ultraviolet absorber is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 100 ppm or more, preferably 200 ppm or more, based on the resin composition (A ′) of the present invention. The upper limit is usually 5 parts by weight or less, preferably 2 parts by weight or less, more preferably 0.5 parts by weight or less. When there is too little content, the effect of a ultraviolet absorber may become small. Moreover, when there is too much content, a manufacturing cost may become high, the heat resistance of a resin composition (A ') and a molding processability may be inferior, and bleeding out of a ultraviolet absorber may arise. . In addition, when using 2 or more types of ultraviolet absorbers together, it is preferable that the total of those usage-amounts satisfy | fill the said range.

  The ultraviolet absorber may be mixed in any process for producing the resin composition (A ′) of the present invention.

(Antistatic agent)
The resin composition (A ′) of the present invention may contain an antistatic agent.

Any antistatic agent can be used as long as the effects of the present invention are not significantly impaired. As a specific example, a surfactant type nonionic, cationic or anionic type is preferable.
One antistatic agent may be used alone, or two or more antistatic agents may be used in any combination and ratio.

  The content of the antistatic agent is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.5% by weight or more, preferably 1% by weight or more with respect to the resin composition (A ′) of the present invention. In addition, it is usually 5% by weight or less, preferably 3% by weight or less. When the content is too small, the effect of improving the antistatic property may be reduced, and when the content is too large, the meltability between the resin compositions (A ′) may be lowered. Furthermore, the surface stickiness of the resin composition (A ′) may occur, and the product value after molding may be reduced.

  The antistatic agent may be mixed in any process for producing the resin composition (A ′) of the present invention.

(Other)
Further, as described above, a lubricant, an antiblocking agent, a release agent, an antifogging agent, a crystal nucleating agent, a colorant, a flame retardant, and the like may be used as additives. Any of these can be used as long as the effects of the present invention are not significantly impaired. Further, the amount used is arbitrary as long as the effects of the present invention are not significantly impaired. Furthermore, any of these additives may be used alone, or two or more may be used in any combination and ratio.

  However, each of the above additives is usually 100 ppm or more, preferably 200 ppm or more, and usually 5 parts by weight or less with respect to the aliphatic polyester resin (A) contained in the resin composition (A ′) of the present invention. Preferably, it is used so as to be 1 part by weight or less, more preferably 0.5 part by weight or less. If the content is too small, the effect of mixing may be reduced. If the content is too large, the production cost may increase, and the heat resistance and molding processability of the resin composition (A ′) may be increased. It may decrease or the bleed out of the additive may occur.

[3. Biodegradable laminated sheet]
The biodegradable laminated sheet of the present invention can be formed into an arbitrary shape by being laminated on a substrate as a resin layer (hereinafter sometimes referred to as a resin layer) containing the above-described resin composition (A ′). It is obtained by molding a sheet. The resin layer may contain other resins, and known fillers such as talc and silica particles. Moreover, it can be used for a biodegradable laminated sheet and its processed product in arbitrary shapes. For example, the biodegradable laminated sheet of the present invention is preferably subjected to secondary processing and used for bags, containers and the like.

(Type of substrate)
The biodegradable laminated sheet of the present invention has a base material for processing into various uses. Although it does not limit as a base material, Usually, the resin-made films and sheets used as an outer layer material etc., the laminated body of aluminum foil and a resin film, non-cloth, cellophane, synthetic paper, paper, etc. are mentioned. As the resin film or resin sheet as a base material, not only a synthetic resin base material such as polypropylene, polyester, polyethylene, or polyamide, but also a film or sheet made of an aliphatic polyester resin such as polylactic acid or polyglycolic acid is used. be able to.

Especially, it is preferable that the base material of the biodegradable laminated sheet of this invention is a thing chosen from paper, a cellophane, a nonwoven fabric, a polylactic acid film, and a polyglycolic acid film. When a biodegradable aliphatic polyester resin film, sheet, paper, or the like is used as the base material, the resulting laminated film becomes biodegradable as a whole, and can form an environmentally friendly packaging material. . Among these, a particularly preferable substrate is a paper substrate. Specific examples of the paper substrate include kraft paper, imitation paper, roll paper, medium quality paper, board, glassine paper, parchment, art paper, board paper, and cardboard base paper. The basis weight of these paper bases (Japanese Industrial Standard JIS P8124) varies depending on the paper quality, but is generally in the range of 10 to 1000 g / m ² , particularly 30 to 700 g / m ² .

(About coating layer)
In addition, as a constituent layer of the biodegradable laminate sheet of the present invention, for example, a coating layer or a coating layer containing a resin diluted with an organic solvent on a substrate (hereinafter referred to as a coating layer) or a gas barrier Other resin layers such as a layer can be arbitrarily set.
As the coating layer on the substrate in the present invention, general-purpose adhesives, organic pigments, inorganic pigments, dyes, binder resins holding pigments, dispersants and the like are preferably used. The coating method is such that the liquid paint is adjusted to 3 to 70% by weight in a solvent such as MEK or toluene and dried. Coating so that the solid amount is ^{0.1g / m 2 ~1g / m 2} , the amount of the preferred upper limit of drying is 0.5 g / ^{m 2} or less, more preferably 0.3 g / ^{m 2} or less, The lower limit is 0.00
1 g / m ² or more, more preferably 0.01 g / m ² or more. Exceeding the upper limit is not preferable because the coating concentration is increased in the coating process or a load is applied to the drying process. Below the lower limit, the adhesive effect is not achieved, which is not preferable. Adhesives include polyether polyurethane polyisocyanate, polyester polyurethane polyisocyanate, one-component reaction type in which an isocyanate group is incorporated at the terminal, polyester-based resins such as polyester polyol and polyester polyurethane polyol, and polyether polyurethane polyols. Two-component reaction type urethane, acrylic resin, nitrocellulose, epoxy resin, phenolic resin, alkyd resin, polyvinyl butyral resin, etc., used by mixing a main component having an ether group hydroxyl group and a curing agent having an isocyanate group Various resins, such as a polymer or a copolymer, can be mentioned, and it is also suitable to use these together. In particular, acrylic resins and polyester resins are excellent for increasing the adhesion between the resin layer and the substrate used in the present invention.

(About resin layer)
In the present invention, the thickness of the resin layer containing the resin composition (A ′) as a main component is arbitrary depending on the purpose of use and the like. The thickness of the resin layer located on the outermost layer of the substrate is usually 2 μm or more, preferably 5 μm or more, more preferably 8 μm or more, and the upper limit is usually 50 μm or less, preferably 30 μm or less, more preferably 20 μm or less. If the thickness of the resin layer exceeds the upper limit, it will not be cooled during laminate production, causing roll troubles, or when punching out a biodegradable laminate sheet, the resin layer will stretch and bearded, or heat seal May worsen sex. On the other hand, when the thickness of the resin layer is below the lower limit, it is difficult to obtain a stable biodegradable laminated sheet having no thickness unevenness, and the required heat seal strength may not be obtained.

(Multilayer structure)
In the present invention, a multilayer structure using a co-extrusion die may be used.
As the layer structure, the coating layer described above is disposed on the substrate as necessary between the above-described base material and the outermost layer, or fat other than the resin composition (A ′) of the present invention as an intermediate layer. It is preferable to arrange a group polyester. Particularly preferred aliphatic polyesters include aliphatic polyesters having low viscosity, aliphatic polyester copolymers having low heat seal expression temperature, high elongation and low elastic modulus, and aliphatic-aromatic polyesters having low elastic modulus. . The typical physical properties are described below.

  The viscosity (MFR) of the intermediate layer used in the present invention is a condition of 190 ° C. and a load of 2.16 kg of the resin composition (A ′) used in the outermost layer for the purpose of increasing the adhesive force between the resin layer and the base material layer. There is no particular limitation as long as it is equal to or lower than the MFR value below. The MFR value under conditions of 190 ° C. and a load of 2.16 kg is usually 2 g / 10 min or more, preferably 5 g / 10 min or more, more preferably 10 g / 10 min or more, and the upper limit is usually 100 g / 10 min or less. Preferably, it is 50 g / 10 min or less, more preferably 30 g / 10 min or less. When exceeding the upper limit, the discharge stability of the extruder is lacking, and the thickness unevenness of the laminated sheet may appear, which is not preferable. Below the lower limit, the effect of strengthening the adhesive strength may not be obtained, which is not preferable.

  The mechanical properties and the like of the intermediate layer used in the present invention are particularly limited as long as they are equal to or less than the elastic modulus of the resin composition (A ′) used in the outermost layer for the purpose of increasing the adhesive force between the resin layer and the base material layer. Not. The upper limit is usually 800 MPa or less, preferably 500 MPa or less, more preferably 300 MPa or less, and the lower limit is usually 10 MPa or more, preferably 50 MPa or more, more preferably 100 MPa or more. When the upper limit is exceeded, the effect of strengthening the adhesive strength may not be obtained, which is not preferable. When the lower limit is not reached, the punchability may be deteriorated.

  Specific preferred resins include, for example, GS Pla AZ71TN, FZ71PD manufactured by Mitsubishi Chemical Co., Ltd., GS Pla AD92WN manufactured by Mitsubishi Chemical Co., Ltd., and Ecoflex manufactured by BASF Co., which are generally referred to as diol units. And a biodegradable polyester having a dicarboxylic acid unit as a main constituent unit. By disposing this intermediate layer, the adhesive strength between the substrate and the resin layer (intermediate layer and outermost layer) is increased, which is preferable. The thickness of the intermediate layer is arbitrary as long as the effects of the present invention are not significantly impaired. Usually, the thickness of the resin layer located on the outermost layer of the substrate is usually 2 μm or more, preferably 5 μm or more, more preferably 8 μm or more, and the upper limit is usually 50 μm or less, preferably 30 μm or less, more preferably 20 μm or less. . If the upper limit is exceeded, the laminate will not be cooled at the time of laminate production, causing roll troubles, or when punching out the biodegradable laminated sheet, the resin layer will stretch and bearded, and the heat sealability will be deteriorated. There is.

Below the lower limit, it may be difficult to obtain a stable biodegradable laminated sheet having no thickness unevenness, or the required heat seal strength may not be obtained.
Usually, the composition ratio of the intermediate layer / outermost layer is 50/50, more preferably 25/75, still more preferably 15/85, and particularly preferably 10/90. When the ratio of the intermediate layer is high, when the biodegradable laminated sheet is punched, the resin layer is stretched and a beard is formed, which is not preferable. On the other hand, when the ratio of the intermediate layer is small, there is a possibility that the effect for obtaining the adhesive strength may not be obtained, and it is difficult to control the thickness unevenness.

(Processing temperature)
In the present invention, the processing temperature of extrusion lamination, particularly the resin temperature immediately below the die, is arbitrarily determined from the relationship between extrusion moldability and adhesiveness, but is usually 300 ° C. or lower, preferably 290 ° C. or lower, and 285 ° C. or lower. On the other hand, the lower limit temperature is 190 ° C. or higher, more preferably 230 ° C. or higher, more preferably 260 ° C. or higher. If the upper limit is exceeded, the melt viscosity of the resin composition (A ′) of the present invention becomes too low, the neck-in becomes large, and when laminating, the sticking to the cooling roll occurs frequently, making molding difficult. is there. When the lower limit is not reached, the motor load of the extruder increases and the apparatus stops. Or the viscosity of a molten film may become high and the adhesive strength to a base material may become low.

(Foam layer)
The biodegradable laminated sheet of the present invention may have a foamed layer, or the laminated resin layer may be foamed. By providing the foamed layer, it is possible to impart a heat insulating and heat retaining effect and an impact absorbing effect. The foam layer can be set by an arbitrary technique. In the biodegradable laminated sheet of the present invention, the resin layer can be foamed by heating and evaporating the moisture contained in the substrate. Specifically, the layered product is placed in a heating oven at the melting point close to the resin to be foamed to give a foamed layer. In the present invention, the resin composition (A ′) having melt tension is a resin composition having excellent foamability. The range of the physical properties of the resin composition corresponding to any of the items described in [2-1], [2-2], etc. is preferable, and when the upper limit is exceeded, a gas such as water vapor expands. If the resin component does not extend and foamability deteriorates or falls below the lower limit, there is no particular tension, and bubbles may not be maintained and may break.

  When a layer containing a resin other than the composition containing the resin composition (A ′) of the present invention is provided, the resin composition described above and / or other resins may be used in any combination and ratio. it can. However, from the viewpoint of the decomposition rate of the biodegradable laminate sheet and the deformability after decomposition, the ratio of the resin having biodegradability to the total resin components contained in the entire biodegradable laminate sheet including the base material and the resin layer However, it is preferable to provide another resin layer so that it may become 50 weight% or more, Preferably it is 70 weight% or more.

  The method for obtaining the biodegradable laminated sheet of the present invention is not particularly limited as long as it satisfies the performance of specific physical properties and the like, and is usually performed. For example, known techniques described in "Latest Laminating Handbook" (1989 Processing Technology Research Society) can be employed. The processing methods are listed as follows: (1) A wet lamination method in which a water-soluble or water-dispersed adhesive is applied to a certain layer, the other layers are laminated together in a wet state, and then dried and wound. 2) A hot melt lamination method in which an adhesive is heated (120 ° C. to 160 ° C.) and applied to a melted layer, another layer is bonded, and then the adhesive is hardened and bonded by instantaneous cooling, (3) There is an extrusion coating method in which a resin is melted and extruded onto a film from a slit die such as a T die, and (4) a resin is melted and extruded onto a film from a slit die such as a T die. Extrusion lamination method, which is a method of coating layers and supplying another layer from an unwinder called a sand feeder and bonding them together (5) T Co-extrusion lamination method that can extrude several kinds of resins with a round die and produce a multilayer film in one step, (6) Apply an adhesive dissolved in an organic solvent on the surface of a layer, dry it, etc. (7) Apply urethane-based adhesive to a layer that has been dissolved by heating without a solvent, and apply another layer by pressing with a heating roll to form a biodegradable laminate sheet. Non-solvent lamination method to be obtained, (8) Thermal lamination method in which a hot melt type, thermosetting type, or thermoplastic type adhesive is impregnated or coated on one layer and the other layer is pressure-bonded with a heating roll. Processing techniques can be used.

  As a method for producing the biodegradable laminated sheet of the present invention, other resins, lubricants, antioxidants, and modifiers added as necessary to the resin layer containing the resin composition (A ′) described above. A method of extruding and laminating a resin composition containing the above-mentioned desired additives such as a nucleating agent on a substrate using a single layer or an extruder having a co-extrusion die (extrusion coating method) A method of obtaining a biodegradable laminate sheet by using an adhesive, flame treatment, thermocompression bonding, etc. after forming the composition containing the resin composition (A ′) of the present invention into a film by inflation molding or T-die film molding is preferable, and productivity From the viewpoint of the physical properties of the obtained biodegradable laminated sheet, the extrusion coating method is particularly preferable. When using the extrusion coating method, use a single layer die usually used for melt extrusion coating and laminating of thermoplastic synthetic resins such as polyethylene, or a melt extrusion coating and laminating device in which coextrusion dies are arranged. Can do.

[3-1. Characteristics of biodegradable laminated sheet and characteristics of its manufacturing process]
The characteristics of the biodegradable laminated sheet and the production process thereof according to the present invention preferably exhibit the following characteristics.
When the state of the molten film is visually confirmed from the die outlet, it is preferable that the biodegradable laminated sheet is transparent, free of lumps, foreign matter and bubbles, and has very little resonance. On the other hand, it is not preferable that the melted film has many spots and foreign matters, or there are many bubbles and many film cracks occur, so that the operation cannot be performed.
The odor can be determined at the time of molding in the present invention, and it is preferable that there is little smoke and no irritating odor. On the contrary, it is not preferable when odor and smoke are seriously generated and there is a serious problem in moldability.

The neck-in can be evaluated by performing trimming in consideration of thickness unevenness of the biodegradable laminated sheet and measuring the product effective width.
That is, in the present invention, the state of the neck-in can be calculated from the standard of the film width and the die width obtained when the air gap is 110 mm in the state of discharge 150 kg / h (the unit of neck-in is mm and To do). Usually, it is 70 mm or more and less than 100 mm, preferably 50 mm or more and less than 70 mm, more preferably less than 50 mm. When the thickness is 100 mm or more, the effective width of the biodegradable laminated sheet as a product is small, so that the productivity is poor, the substrate width is limited, and the substrate loss is increased by trimming the substrate. Tend. Therefore, it is preferable that the neck-in value is small. However, the numerical value of this neck-in may change in resin characteristics such as die width, air gap, discharge amount, take-up speed, and the like.

  The roll-off property in the present invention can be evaluated by confirming the situation when a biodegradable laminated sheet is produced at a temperature of 20 degrees with a semi-matt processing roll. Preferably, it is in a state that does not cause any problem in the roll-off property. In particular, it is preferable that the production speed is in a state where machining can be performed up to 80 m / min to 180 m / min. When the roll and the sheet laminate are in a tendency to adhere to each other when the roll-off property is poor, if the tendency is strong when the laminate is peeled off from the roll, the substrate and the resin layer are peeled off or the substrate is broken. It is not preferable when it cannot be produced by being wound on a roll.

  The motor load can be determined at the time of molding, and is determined by the motor load value (%) of the extruder. Normally, it is not necessary to stop the motor capacity during production. The motor load value is preferably 95% or less, more preferably 90% or less, and even more preferably 85% or less. If the load is excessively applied, the motor may stop during production, which is not preferable.

  In the present invention, when the appearance of the biodegradable laminated sheet is confirmed by visual observation or touch of the resin layer, the cooling roll is transferred, and the resin layer of the biodegradable laminated sheet is in a state where there is no unevenness due to FE or the cooling roll It is in a state of being followed when it is peeled off, but it is preferably in a state that does not cause any problem. Conversely, when the resin layer of the biodegradable laminate sheet is peeled off from the cooling roll, wrinkles are generated when the resin layer is slightly stretched, or it is in a peeled state between the resin layer and the base material layer, and a state where the adhesive strength is weak is preferable. Absent.

  The adhesive strength between the resin layer and the paper substrate of the present invention can be evaluated by measuring by the adhesive strength measuring method described below, and observing the state of peeling between the resin layer and the paper. The preferred adhesion state is at a level that does not cause any problem in practical use, as long as cohesive failure of the paper that does not peel at the interface and has some paper peeling is observed, and more preferably, the paper does not peel at the interface and cohesive failure of the paper. If it is observed evenly. On the contrary, the adhesive strength between the resin layer and the substrate is a weak level, interface peeling is observed, and the adhesive strength between the resin layer and the substrate is 50 g / 15 mm in the width direction. In the following, the state of pseudo-adhesion is not preferable. If there is a lot of unevenness in the pseudo-adhesion and adhesive strength, the punchability and heat-sealability in the secondary processing process tend to deteriorate. There is a possibility of leakage and the like, which is not preferable.

In the present invention, the punchability is most preferable if the resin layer has no beard or the resin layer has a slight beard. Moreover, the state where the whisker of the resin layer appears as a whole and the punched pieces are stuck with a probability of 20% or less may be used. On the contrary, it is not preferable that the punched pieces stick together at 20% or more in a state where the whiskers of the resin layer appear as a whole. This evaluation can be confirmed by the following simple evaluation method for punchability. If the beard appears, 2
This is because the punched piece does not move away from the blank (outside of the punched piece) at the time of punching in the next processing, and causes troubles due to poor feeding in the next process.

  The biodegradable laminated sheet of the present invention has a feature of good heat sealability, is easy to perform secondary molding processing such as paper cups and bags, and is high-speed molding (110 to 100 cps / min in cup molding) or automatic. Suitable for filling machines. The heat seal strength between the resin layers of the laminate of the present invention is at least 5 N / 15 mm or more, and the upper limit is preferably 25 N / 15 mm or less. Below the lower limit, peeling proceeds with a very weak force, and the peeling type is also interfacial peeling, the adhesive strength is weak, and it is not practical as a packaging material such as breaking the bag. On the other hand, when the value exceeds the upper limit value, it is necessary to set the seal pressure, the seal time, and the seal temperature higher than usual, which is not preferable because the productivity during the secondary processing may be lowered. Moreover, the heat-seal expression temperature of the laminated body of this invention should just be 80 to 150 degreeC. If the temperature is lower than this temperature, it is difficult to obtain heat resistance when used as a container such as a cup, and when a liquid such as hot water is added, the seal portion is peeled off, which may cause liquid leakage. On the other hand, if the upper limit is exceeded, it is not preferable because it requires extending the heat sealing time and increasing the heat sealing pressure. The heat seal strength can be confirmed by the following method.

[3-2. Use of biodegradable laminated sheet]
(Secondary processed product)
The biodegradable laminated sheet obtained in the present invention can be subjected to secondary processing into various packaging materials, bag making, cups, trays, cartons and the like. Various types of processing are the same as conventional paper and plastic laminated paper, that is, automatic packaging machines such as three-side seal automatic bag making machines, center seal automatic bag making machines, and standing pouch automatic bag making machines as packaging materials. , Pillow-type automatic filling and packaging machines, three-side seal filling and packaging machines, four-side seal filling and packaging machines and other automatic filling and packaging machines such as flat bags, square bottom bags, turtle shell bags, etc. It can be processed into a shape. Furthermore, it can also process using apparatuses, such as a paper cup molding machine, a punching machine, a sack pasting machine, and a box making machine. In these processing machines, the biodegradable laminated sheet is bonded by a known technique. Generally, the heat sealing method, the impulse sealing method, the ultrasonic sealing method, the high frequency sealing method, the hot air sealing method, the frame sealing method are used. Etc. are adopted.

Although the heat seal setting temperature of the biodegradable laminated sheet of the present invention varies depending on the adhesion method, when using a heat-type heat seal tester having a seal bar and using a paper substrate of 100 to 300 g / m ² or more, The upper limit value is not particularly set as long as it is equal to or higher than the heat seal expression temperature (rise temperature), but is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 180 ° C. or lower. If it is below the lower limit, it may not be adhered, which is not preferable. On the other hand, if the value exceeds the upper limit value, the resin is also melted by heating in the vicinity of the seal portion, the film pressure of the resin layer is thinned, and the seal strength may be reduced.

  The heat seal setting pressure of the biodegradable laminated sheet of the present invention varies depending on the adhesion method, but when a heating heat seal tester having a seal bar is used, it may be 0.05 MPa or more, preferably 0.1 MPa or more. . The upper limit is 0.5 MPa or less, preferably 0.45 MPa or less, more preferably 0.4 MPa or less. If it is below the lower limit, it may not be adhered, which is not preferable. On the other hand, if the upper limit is exceeded, the membrane pressure at the end of the seal may be reduced, and the seal strength may be reduced.

  The heat seal setting time of the biodegradable laminated sheet of the present invention varies depending on the adhesion method, but when a heating heat seal tester having a seal bar is used, it should be 0.25 seconds or more, preferably 0.5 seconds or more. That's fine. The upper limit is 3 seconds or less, preferably 2 seconds or less, more preferably 1.5 seconds or less. If it is below the lower limit, it may not be adhered, which is not preferable. On the other hand, if the value exceeds the upper limit, the film pressure at the end of the seal may be thinned and the seal strength may be reduced.

(Use of concrete processed products)
The biodegradable laminated sheet according to the present invention is used for packaging container materials, agricultural / civil engineering / fishery materials, and the like by processing.

  Examples of packaging container materials include shopping bags, various bag making, magnetic tape cassette product packaging materials such as video and audio, flexible disk packaging materials, plate making materials, packaging bands, adhesive tapes, tapes, yarns, cups, trays, Applicable to cartons, lunch boxes, prepared food containers, food and confectionery packaging materials, food wrap materials, cosmetic and cosmetic wrap materials, diapers, sanitary napkins, pharmaceutical wrap materials, pharmaceutical packaging materials, stiff shoulders, sprains, etc. Various packaging materials such as foods, electronics, medical care, medicines, cosmetics and the like such as packaging materials for surgical patches to be used.

  As materials for agriculture, civil engineering and fisheries, for example, films for agriculture and horticulture, wrap films for agricultural chemicals, greenhouse films, fertilizer bags, seedling pots, waterproof sheets, sandbag bags, architectural films, weed prevention sheets And materials used in agriculture, civil engineering and fisheries, such as vegetation nets made of tape and yarn. In addition, it can be applied as a blow-molded product, and can be used as a garbage bag or a compost bag, and can be suitably used as a material in a wide range.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples without departing from the gist thereof.

[1. Physical property measurement method]
[1-1. MFR and MVR]
MVR and MFR, which are melt flow volumes, were measured according to the method of JIS-K7210 using a Takara Industries melt indexer.

Specifically, MVR (2.16) and MVR (10.0) were measured by subjecting aliphatic polyester resin (A) dried at 80 ° C. for 12 hours to a melt indexer. The conditions for melt indexer, melt flow volume per unit time measured under a load 10.0kg at 190 ° C. The (cm ^3/10 min) and MVR (10.0), load 2.1 190 ° C.
Melt flow volume per unit time measured at 6kg a (cm ^3/10 min) MVR (2.16
). A value obtained by dividing the value of MVR (2.16) by the value of MVR (10.0) was defined as MVR-R.

  Moreover, MFR was measured by using the aliphatic polyester resin (A) dried at 80 degreeC for 12 hours for a melt indexer. The melt indexer condition was 190 ° C. with a load of 2.16 kg, and the melt flow weight per unit time (g / 10 minutes) measured under this condition was taken as the MFR value.

[1-2. Terminal carboxyl group content]
The amount (μmol / g) of the carboxyl group present at the terminal was measured by dissolving the aliphatic polyester resin (A) in benzyl alcohol and performing neutralization titration with a 0.1N sodium hydroxide aqueous solution.

[1-3. Reduced viscosity]
The reduced viscosity (η _sp / c) at 30 ° C. of the aliphatic polyester resin (A) of the present invention was measured using an Ubbelohde viscosity tube. Specifically, the aliphatic polyester resin (A) is dissolved in a phenol / tetrachloroethane (1: 1 weight ratio) solvent so as to be 0.5 g / dl, and the aliphatic polyester resin (A) solution at 30 ° C. The solution viscosity was measured with an Ubbelohde viscosity tube.

[NMR measurement conditions]
^{Using 1} H-NMR, the amount of terminal hydroxyl groups, the amount of terminal vinyl groups, the quantification of aliphatic unsaturated dicarboxylic acid units (8) and (9), and the contained aliphatic hydroxycarboxylic acid unit (3) were quantified. A solution obtained by dissolving 20 mg of polymer in 0.6 ml of deuterated chloroform was used as a measurement sample, and ¹ H at room temperature using an Avance 400 spectrometer manufactured by Bruker BioSpin.
-NMR spectra were measured and quantified. The flip angle is 45 degrees, the data capture time is 4 seconds, the waiting time is 6 seconds, and the number of integrations is 256. The exponential function of LB (Line Broadening) = 0.1 Hz was used for the window function, and Fourier transform processing was performed.

[1-4. Terminal hydroxyl group content]
The hydroxyl group present at the end of the aliphatic polyester resin (A) (that is, the terminal hydroxyl group) is converted into methylene on the carbon atom to which the terminal hydroxyl group appearing near 3.66 ppm is directly bonded using ¹ H-NMR. Quantified by proton peak.

[1-5. Terminal vinyl group content]
The amount of the vinyl group (that is, the terminal vinyl group) present at the terminal of the aliphatic polyester resin (A) is about 5.15 ppm or about 5.78 ppm using ¹ H-NMR. It quantified by the peak of the proton on the carbon atom which forms the double bond which exists in the terminal of resin (A).

[1-6. Determination of Aliphatic Unsaturated Dicarboxylic Acid Units (8) and (9)]
The amount of the aliphatic unsaturated dicarboxylic acid unit (8) was determined by 6.85 pp using ¹ H-NMR.
Quantification was performed by a proton peak on a carbon atom forming a double bond in the unit appearing near m. In addition, the aliphatic unsaturated dicarboxylic acid unit (9) is quantified by ¹ H-NMR, based on the proton peak on the carbon atom forming a double bond in the unit that appears in the vicinity of 6.25 ppm. did.

[1-7. Amount of aliphatic hydroxycarboxylic acid unit (3) contained]
The quantification of the aliphatic hydroxycarboxylic acid unit (3) was performed using ¹ H-NMR. When the hydroxyl group of the unit formed an ester bond to form a branched chain, it was quantified by the peak of methine proton in the unit appearing around 5.47 ppm, and when not reacting, around 4.49 ppm.

[1-8. YI value]
YI value is obtained by filling pellet-shaped aliphatic polyester resin (A) into a cylindrical powder measurement cell having an inner diameter of 30 mm and a depth of 12 mm, and using a colorimetric color difference meter Color Meter ZE2000 (Nippon Denshoku Industries Co., Ltd.) And it measured based on the method of JISK7105. The measurement cell was rotated by 90 degrees by the reflection method and obtained as a simple average value of values measured at four points.

[1-7. Melt tension]
The melt tension was measured according to the method described in the above (melt tension).

[1-8. Melt viscosity]
The melt viscosity was measured according to the method described in the above (melt viscosity).

[1-10. Gel content]
The gel content was measured according to the method described above (gel content).

[1-11 Appearance and stability of molten film]
The state of the molten film was visually observed from the die outlet.
(Double-circle): It is a normal state with a transparent molten film, and there are no blisters, foreign materials, and bubbles.
There is also very little resonance.
○: The molten film is transparent, there are few irregularities, foreign matters, and bubbles, and the resonance is within a range that allows the molding at a level that does not cause a problem.
(Triangle | delta): A molten film is opaque and it is in a state with many spots and foreign materials. There are also many resonances.
X: The molten film is in a state in which there are many spots and foreign matters, or there are many bubbles and many film cracks occur, so that the operation cannot be performed.

[1-12 Odor]
In the present invention, the odor during molding was determined.
A: Little smoke and no pungent odor.
○: Smoke is low, and some odors are observed, but this is not a problem.
Δ: Although there are some problems, it is a moldable level.
X: There is a serious problem in moldability.

[1-13 Neck-in]
Trimming was performed in consideration of uneven thickness of the biodegradable laminated sheet, and the effective width of the product was measured. In the present invention, confirmation of the neck-in condition was calculated from the standard of the film width and the die width obtained when the air gap was 110 mm with the discharge being 150 kg / h. The unit of neck-in is mm.
A: Less than 50 mm.
○: 50 mm or more and less than 70 mm.
Δ: 70 mm or more and less than 100 mm
×: 100 mm or more

[1-14 Separation roll property]
The separation property in the present invention was confirmed by the situation when a biodegradable laminated sheet was produced at a temperature of 20 degrees with a semi-matt processing roll.
(Double-circle): The state which does not become a problem at all in roll-off property.
○: There is a problem in the roll-off property to some extent, and it can be processed up to a production speed of 180 m / min.
Δ: The roll is slightly sticky but can be produced.
X: A state where the production is possible, but the production rate is 100 m / min or more, and the substrate sticks to the roll and the substrate breaks.

[1-15 Motor load status]
The motor load in the present invention is indicated by the main motor (the outermost resin extruder).
[1-16 Overview of Resin Layer of Biodegradable Laminated Sheet]
In the present invention, the resin layer side of the obtained biodegradable laminated sheet was confirmed by visual and evaluation by touch feeling.
(Double-circle): The state by which the cooling roll was transferred and there was no unevenness by FE.
○: The cooling roll is transferred and there is a slight unevenness due to FE.
Δ: A state in which the resin layer of the biodegradable laminated sheet is attached when the resin layer is peeled off from the cooling roll, but is not particularly problematic.
X: When the resin layer of a biodegradable laminated sheet peels from a cooling roll, it is in the state which the resin layer extended a little, and the state where adhesive strength is weak.

[1-17 Adhesive strength]
The adhesive strength between the resin layer and the paper substrate was shown as the strength when peeled at a peeling angle of 180 °, a peeling speed of 300 mm / min, and a test piece width of 15 mm, and the state of peeling between the resin layer and paper was observed.
A: Interface peeling did not occur, and cohesive failure of the paper was observed evenly.
○: Although there is no problem in practical use, the interface does not peel off, and cohesive failure of the paper with slight paper peeling is observed. Δ: The adhesive strength between the resin layer and the substrate is weak, and the interface peels off. In addition, in the width direction, there is much unevenness in adhesive strength.
X: The adhesive strength between the resin layer and the substrate is 50 g / 15 mm or less and is in a pseudo-adhesive state.

[1-18 Punchability of biodegradable laminated sheet]
In the present invention, the punchability was confirmed by hitting a male blade from the paper surface by a punching punch with a stationery. The number of punches was 20 times.
(Double-circle): The situation where the beard of a resin layer does not appear.
○: Slight whisker of resin layer appears.
Δ: The state in which the whisker of the resin layer appears as a whole, and the punched pieces stick to each other at 20% or less. ×: The state in which the whisker of the resin layer appears as a whole, and the punched pieces stick to it at 20% or more.

[1-19 Heat Sealability of Biodegradable Laminated Sheet]
The heat sealability of the biodegradable laminated sheet of the present invention was determined as the heat seal strength according to JIS Z 1526. Regarding the preparation of the test piece and the measurement of the heat seal strength, a sample which was allowed to stand at 23 ° C. and 50% RH for 1 day or longer was used as a condition adjustment of the sample.
As a test piece, use a flat part with a membrane pressure of 20 μm as the test piece, cut out vertically and horizontally 15 cm, heat seal one end with a heat sealer so that the resin layer part is aligned, and form a strip with a width of 15 mm. What was cut out was used. At this time, the one sealed at right angles to the film flow direction was defined as the longitudinal seal strength. On the contrary, what was sealed parallel to the film flow direction was defined as the transverse seal strength.
The heat seal was performed using a single-sided heating bar sealer with a seal bar width of 5 mm, the seal temperature was arbitrary, the seal pressure was 0.4 MPa, the seal time was 1 second, and the temperature at which the seal part was completely adhered was entered. The term “complete adhesion” as used herein refers to a state in which not only the interfacial peeling between the resin surfaces but also part of the fiber peeling is seen. Or it is the temperature at which the heat seal strength starts to saturate in the high temperature region (obviously complete adhesion).

[2. Aliphatic polyester resin (A)]
As the aliphatic polyester resin (A), the following three types obtained using the catalysts described below were used.

[2-1. Preparation of catalyst for polycondensation reaction]
62.0 g of magnesium acetate tetrahydrate was put into a 500 ml glass eggplant-shaped flask equipped with a stirrer, and 250 g of absolute ethanol (purity 99% or more) was further added. Further, 35.8 g of ethyl acid phosphate (mixing weight ratio of monoester and diester was 45:55) was added and stirred at 23 ° C. After confirming that magnesium acetate was completely dissolved after 15 minutes, 75.0 g of tetra-n-butyl titanate was added. Stirring was further continued for 10 minutes to obtain a uniform mixed solution.

  This mixed solution was transferred to a 1 L eggplant-shaped flask, and concentrated under reduced pressure by an evaporator in an oil bath at 60 ° C. After about 1 hour, most of the ethanol was distilled off, leaving a translucent viscous liquid. The temperature of the oil bath was further increased to 80 ° C., and further concentration was performed under a reduced pressure of 5 Torr. The viscous liquid gradually changed from the surface to a powder form, and was completely pulverized after about 2 hours. Then, it returned to normal pressure using nitrogen, and it cooled to room temperature, and obtained 108 g of pale yellow powder.

A sample obtained by subjecting a metal element contained in the obtained catalyst to 0.1 g of a sample obtained by wet decomposition with hydrogen peroxide in a Kjeldahl flask in the presence of sulfuric acid and then with a constant volume of distilled water was used. As a result of quantitative analysis using ICP-AES ULTRACE JY-138U type manufactured by YVON, the titanium atom (T) content was 10.3 wt%, the Mg atom (M) content was 6.8 wt%, and the phosphorus atom The (P) content was 8.7% by weight, and the molar ratios were T / P = 0.78 and M / P = 1.0. In addition, the weight after the reaction was reduced by 37% of the total weight of the raw material excluding the ethanol solvent, compared with the weight before the reaction. Further, the powdery catalyst was dissolved in 1,4-butanediol so that the titanium atom content was 34000 ppm. The storage stability of the catalyst in 1,4-butanediol was good, and in the catalyst solution stored at 40 ° C. in a nitrogen atmosphere, no precipitate was observed for at least 40 days. The catalyst solution had a pH of 6.1. In this catalyst solution, no absorption derived from alkoxide groups of butanol or 1,4-butanediol was observed on ¹ H-NMR, and no organic alkoxide group was bonded to the titanium metal of the catalyst. found.

[2-2. Production example]
[2-2-1. Production of Aliphatic Polyester Resin (A) (A-1) (Production Example 1)]
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and an exhaust port for decompression, 100.3 parts by weight of succinic acid, 99.5 parts by weight of 1,4-butanediol, 0. 37 parts by weight were charged, and the inside of the system was put into a nitrogen atmosphere by nitrogen-vacuum substitution. While stirring the system, the temperature was raised to 230 ° C. over 1 hour and the reaction was carried out at this temperature for 1 hour. Thereafter, the above catalyst solution was added. The amount added was such that the titanium atoms were 50 ppm relative to the weight of the resulting aliphatic polyester resin (A). The temperature was raised to 250 ° C. over 280 minutes, the pressure was reduced to 0.7 hPa at the same time, and the reaction was carried out for 5.6 hours from the start of pressure reduction to obtain an aliphatic polyester resin (A) (A-1).

  At this time, the average pressure reduction rate from normal pressure to 2 hPa was 7.9 hPa / min. The amount of decrease in polymer temperature when the pressure was changed between 100 hPa and 10 hPa in the reaction system was 2.3 ° C. It was possible to produce the aliphatic polyester resin (A) while maintaining a low reactivity with a small decrease in the polymer temperature during the pressure drop.

The obtained aliphatic polyester resin (A) (A-1) had a reduced viscosity of 2.4 dL / g, and a white aliphatic polyester resin (A) (YI value: 2.5) was obtained. The value of MVR (2.16) at 190 ° C. is 3.6 cm ^3/10 min, the value of MVR (10.0) is 38.6cm ^3/10 min, the value of MVR (2.16), MVR The value of MVR-R divided by the value of (10.0) was 10.7. The amount of terminal carboxyl groups of the obtained aliphatic polyester resin (A) (A-1) was 51 μmol / g. The unit derived from malic acid is 0.082 mol%, the unit derived from fumaric acid is 0.024 mol%, and the unit derived from maleic acid is 0.0075 mol% with respect to all copolymer units, Their total was 0.11 mol%. At this time, the amount of the unit derived from malic acid was 2.6 as a molar ratio to the total amount of the unit derived from fumaric acid and the unit derived from maleic acid. Furthermore, the amount of units derived from fumaric acid was 3.2 as a molar ratio to the amount of units derived from maleic acid. Furthermore, the amount of terminal vinyl groups was 0.095 mol%. The resulting aliphatic polyester resin (A) (A-1) has a MFR of as low as 2.6 g / 10 min at 190 ° C. and a load of 2.16 kg, and has a good melt tension for molding films and containers. It was resin which has. Other physical properties measured are shown in Tables 2 and 3.

[2-2-2. Production of Aliphatic Polyester Resin (A) (A-2) (Production Example 2)]
The average pressure reduction rate from normal pressure to 2 hPa is 12.8 hPa / min, the amount of decrease in polymer temperature when the pressure in the reaction system is changed between 100 hPa and 10 hPa is 7.3 ° C. Manufacture was performed under the same conditions as in Production Example 1 except that the reaction was performed for 5.2 hours to obtain an aliphatic polyester resin (A) (A-2).

The reduced viscosity of the obtained polyester resin (A-2) was 1.9 dL / g, and white polyester (YI value: 3.9) was obtained. Value of MVR (2.16) 35 cm ^3/10 min, the value of MVR (10.0) is 350 cm ^3/10 min, the value of MVR (2.16), the value of MVR (10.0) The value of MVR-R divided by 10 was 10. The amount of terminal carboxyl groups of the obtained aliphatic polyester resins (A) and (A-2) was 49 μmol / g. The unit derived from malic acid is 0.072 mol%, the unit derived from fumaric acid is 0.022 mol%, and the unit derived from maleic acid is 0.0055 mol% with respect to all copolymer units, Their total was 0.10 mol%. At this time, the amount of the unit derived from malic acid was 2.6 as a molar ratio to the total amount of the unit derived from fumaric acid and the unit derived from maleic acid. Furthermore, the amount of units derived from fumaric acid was 4.0 as a molar ratio to the amount of units derived from maleic acid. Furthermore, the amount of terminal vinyl groups was 0.102 mol%. The obtained aliphatic polyester (A-2) has a high MFR of 18.7 g / 10 min under the conditions of 190 ° C. and a load of 2.16 kg, and has a low motor load in T-die molding or Y injection molding. It was a resin with excellent moldability. The other measured physical properties are shown in Tables 1 to 3.

[2-2-3. Production of Aliphatic Polyester Resin (A) (A-3) (Production Example 3)]
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and an exhaust port for decompression, 100.3 parts by weight of succinic acid, 88.8 parts by weight of 1,4-butanediol, 0. 37 parts by weight and 5.4 parts by weight of an aqueous 88% lactic acid solution in which germanium dioxide as a catalyst was previously dissolved at 0.98% by weight were charged, and the system was placed in a nitrogen atmosphere by nitrogen-vacuum substitution. While stirring the system, the temperature was raised to 220 ° C. over 1 hour, and the reaction was carried out at this temperature for 1 hour. Next, the temperature was raised to 230 ° C. over 160 minutes, and at the same time, the pressure was reduced to 0.7 hPa and reacted for 5.4 hours from the start of pressure reduction to obtain an aliphatic polyester resin (A) (A-3).

  At this time, the average pressure reduction rate from normal pressure to 2 hPa was 12.8 hPa / min. The amount of decrease in the polymer temperature in the reaction system when the pressure was changed between 100 hPa and 10 hPa in the reaction system was less than 1 ° C.

The resulting aliphatic polyester resin (A) (A-3) had a reduced viscosity of 2.5 dL / g, and a white aliphatic polyester resin (A) (YI value: 0.5) was obtained. Value of MVR (2.16) 5.1 cm ^3/10 min, the value of MVR (10.0) is 50.5cm ^3/10 min, the value of MVR (2.16), MVR (10 . The value of MVR-R divided by the value of 0) was 9.9. The amount of terminal carboxyl groups of the obtained aliphatic polyester resin (A) (A-3) was 26 μmol / g. The unit derived from malic acid is 0.097 mol%, the unit derived from fumaric acid is 0.011 mol%, and the unit derived from maleic acid is 0.0012 mol% with respect to all copolymer units, Their total was 0.11 mol%. At this time, the amount of units derived from malic acid was 8.0 as a molar ratio to the total amount of units derived from fumaric acid and units derived from maleic acid. Furthermore, the amount of units derived from fumaric acid was 9.2 as a molar ratio to the amount of units derived from maleic acid. Further, the obtained aliphatic polyester resin (A) (A-3) has a MFR of as low as 3.3 g / 10 min under the conditions of 190 ° C. and a load of 2.16 kg, and it is a good melt for molding films and containers. It was a resin with tension. The other measured physical properties are shown in Tables 1 to 3.

[3. Organic peroxide (B)]
As the organic peroxide (B), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Nippon Yushi Perhexa 25B; molecular formula C ₁₆ H ₃₄ O ₄ , molecular weight 290.45)
) Was used.

[4. Production of Resin Composition (A ′)]
[Production Example 4]
100 parts by weight of the aliphatic polyester resin (A) (A-1) and 0.0001 part by weight of the organic peroxide (B) were mixed using a Henschel mixer (see Table 1). The obtained mixture was melt-kneaded at a temperature of 190 ° C. and a screw rotation speed of 150 rpm using a twin-screw extruder, and the strand was cooled with water and cut to obtain a white resin composition (A ′). Thereafter, pellets of the resin composition (A ′) were dried at 70 ° C. in a nitrogen atmosphere for 8 hours. When the physical properties of the resin compositions (A ′) and (A′-1) were measured, they were as shown in Table-2 and Table-3.

[Production Examples 5-8, 10, 11]
In the same manner as in Production Example 4, the amount of the organic peroxide (B) is changed to the amount described in Table 1, and the resin composition (A ′) (A′-2 to A′-5, A '-7, A'-8) was obtained. The physical property values are shown in Table-1 to Table-3.

[Production Example 9]
The same procedure as in Production Example 4 except that the aliphatic polyester resin (A) used was an aliphatic polyester resin (A) (A-2) and the amount of the organic peroxide (B) was 0.0015 parts by weight. The resin composition (A ′) (A′-6) was obtained. The physical property values are shown in Table-1 to Table-3.

[5. Production of biodegradable laminated sheet]
[Example 1]
The resin composition (A′-1) in Production Example 4 contains an antioxidant (Irganox 1330 500 ppm), a 360 mm wide hanger coat type T die is used in a single screw extruder with a screw diameter of 40 mmΦ, and a cylinder set temperature is set. C1 (hopper side temperature) 230 ° C, C2 (die side temperature) 280 ° C, die part temperature (end 250 ° C, center 270 ° C, end 250 ° C), resin is extruded, and discharge is constant at an extruder rotation speed of 100rpm And waited for the stability of the molten film. After stabilization, the resin temperature (265 ° C.) immediately below the center of the die and the resin temperature at both ends (250 ° C.) were measured, and film stability and odor were observed. Paperboard (250 g / m ² ) was fed out as a base material from a low speed and laminated with a molten resin. The machining speed was gradually increased and operation was performed at 100 m / min. The base material is subjected to corona treatment, and the film thickness is 20 μm (average of three points in the width direction, 23 μm, 20 μm, 22 μm) while finely adjusting the feeding speed, the rotational speed of the extruder, and the die temperature (both ends and center). A biodegradable laminated sheet was obtained by laminating a molten resin film so that The air gap was 110 mm, a semi-matt roll was used as the cooling roll, the cooling temperature was 20 ° C., and the nip roll pressure was set to 0.4 MPa. Regarding the laminating processability, overview of molten film, neck-in, roll-off property, motor load (%), overview of laminated product, uneven thickness in the width direction, thickness, adhesive strength and peeled state, heat sealability, punchability It was described in 4.

[Examples 2 to 6]
The resin composition (A′-2 to A′-6) synthesized in the above production example was changed in the same manner as in Example 1, and the resin composition was laminated on the substrate. In each example, the resin temperature was changed in consideration of processability. The results are shown in Table-4.

[Example 7]
The resin composition (A′-5) of Production Example 8 and the aliphatic polyester (A-1) of Production Example 1 were dry blended at 8: 2, and an antioxidant (Irganox 1330 500 ppm) was included, and the screw diameter was 40 mmΦ. Using a 360 mm wide hanger coat type T die in a single screw extruder, C1 (hopper side temperature) 230 ° C, C2 (die side temperature) 280 ° C, die temperature (end 250 ° C, center 270 ° C) The temperature was set to 250 ° C. at the end, the resin was extruded, the discharge was kept constant at an extruder rotation speed of 100 rpm, and the molten film was allowed to stabilize. After stabilization, the resin temperature (265 ° C.) immediately below the center of the die and the resin temperature (250 ° C.) at both ends were measured, and film stability and odor were observed. Paperboard (250 g / m ² ) was fed out as a base material from a low speed and laminated with a molten resin. The machining speed was gradually increased and operation was performed at 100 m / min. The base material is subjected to corona treatment, and the film thickness is 22 μm (average in three positions in the width direction, 23 μm, 22 μm, and 22 μm) while finely adjusting the feeding speed, the number of revolutions of the extruder, and the die temperature (both ends and center). A biodegradable laminated sheet was obtained. The results are shown in Table-4.

[Example 8]
A laminate biodegradable laminated sheet was obtained by changing the blend ratio of the resin composition of Example 7 and the aliphatic polyester of Production Example 1 from 8: 2 to 5: 5. The results are shown in Table-4.

[Example 9]
The aliphatic polyester (A-1) of Example 7 was changed to the aliphatic polyester (A-2).
Moreover, since the molecular weight was low, the temperature was changed to 240 ° C. as processing conditions.
The results are shown in Table-4.

[Example 10]
A biodegradable laminated sheet was produced at a speed of 100 m / min using a two-type two-layer coextrusion molding machine (die width; 360 mm, multi-manihold type coextrusion laminator). AZ71TD is used for the intermediate layer, and the resin composition (A′-5) of Production Example 8 and the aliphatic polyester (A-1) of Production Example 1 are dry blended at 8: 2 in the outermost layer, and an antioxidant (Irganox 1330 500 ppm). The cylinder set temperature is set to C1 (hopper side temperature) 230 ° C, C2 (die side temperature) 280 ° C, and die part temperature (end 250 ° C, center 270 ° C, end 250 ° C), melting at constant discharge Waited for the film to stabilize. After stabilization, the resin temperature (265 ° C.) immediately below the center of the die and the resin temperature at both ends (250 ° C.) were measured, and film stability and odor were observed. Paperboard (250 g / m ² ) was fed out as a base material from a low speed and laminated with a molten resin. The machining speed was gradually increased and operation was performed at 100 m / min. The base material is subjected to corona treatment, and the film thickness is 25 μm (average in three positions in the width direction, 26 μm, 24 μm, 25 μm) while finely adjusting the feeding speed, the rotational speed of the extruder, and the die temperature (both ends and center). A biodegradable laminated sheet was obtained by laminating a molten resin film so that The composition ratio of the resin layer was 6 μm for the intermediate layer. The air gap was 110 mm, a semi-matt roll was used as the cooling roll, the cooling temperature was 20 ° C., and the nip roll pressure was set to 0.4 MPa. Regarding laminating processability, overview of molten film, neck-in, roll-off property, motor load (%), appearance of laminated product, thickness unevenness in the width direction, thickness, adhesive strength and peeled state, heat sealability, punchability- 4.

[Example 11]
A biodegradable laminated sheet was obtained by setting the polybutylene succinate adipate copolymer to 6 μm in the intermediate layer of Example 10. The results are shown in Table-4.

[Comparative Example 1]
In the same manner as in Example 1, a biodegradable laminated sheet was obtained using an aliphatic polyester (A-3) as the resin layer.
The results are shown in Table-4. Compared with each example, since the aliphatic polyester has a less branched structure, the melt tension, which is a factor for improving moldability, is insufficient. It can be seen that the roll property is remarkably deteriorated.

[Comparative Example 2]
Under the same conditions as in Example 9, a biodegradable laminate sheet was obtained using the aliphatic polyester (A-2) as the resin layer. Compared with Example 9 in which the aliphatic polyester resin composition (A ′) with improved moldability was blended, the deterioration of neck-in and the roll-off property were deteriorated, and it was difficult to operate continuously.

[Comparative Example 3]
In the same manner as in Example 1, the aliphatic polyester resin composition (A′-7) in Production Example 10 was changed to obtain a biodegradable laminated sheet.
When each example is compared, it turns out that neck-in, roll-off property, and adhesive strength are getting worse.

[Comparative Example 4]
The biodegradable laminated sheet was obtained by changing to the aliphatic polyester resin composition (A′-8) of Production Example 11 in the same manner as in Example 1.
When the examples were compared, it was observed that the motor load and the molten film had a poor appearance, the laminated product had a poor appearance, and that the adhesive strength was lowered.

(Foaming experiment)
[Example 12]
The biodegradable laminated sheet obtained in Example 4 was placed in an oven at 120 ° C. and held for 5 minutes. After that, when the foaming state was confirmed, a foamed layer was formed on the resin layer.

[Comparative Example 5]
When the foamability of the biodegradable laminated sheets obtained in Comparative Examples 1 and 4 was confirmed by the method of Example 12, the biodegradable laminated sheet of Comparative Example 1 was in a state in which a hole was opened and no bubbles were retained. Met. The biodegradable laminated sheet of Comparative Example 4 was in a state where the base material layer and the resin layer were peeled off without foaming.

* Note: In the table, “(3) + (4) + (5)” is the unit represented by the formula (3), the unit represented by the formula (4), and the formula (5). Represents the total percentage of units. Further, “x or y” represents a value obtained by dividing the total proportion (a) of the aliphatic unsaturated dicarboxylic acid units by the total proportion (b) of the aliphatic hydroxycarboxylic acid units.

* Note In the table, “10 s ⁻¹ [Pa · s]” represents the melt viscosity at a temperature of 190 ° C. and a shear rate of 10 s ⁻¹ , and “1000 s ⁻¹ [Pa · s]” represents the temperature 190 It represents the melt viscosity at ⁰ ° C. and a shear rate of 1000 s ⁻¹ .

The use of the biodegradable laminated sheet of the present invention is not particularly limited, and can be used for various known uses. Specific examples include those widely used in packaging container materials, agricultural / civil engineering / fishery materials.

Claims (4)

A method for producing a biodegradable laminate sheet obtained by laminating a resin composition obtained by mixing an aliphatic polyester resin and an organic peroxide on a substrate,
The aliphatic polyester resin comprises an aliphatic dicarboxylic acid unit represented by the following formula (1), an aliphatic diol unit represented by the following formula (2), and an aliphatic hydroxy represented by the following formula (3). One or more aliphatic hydroxycarboxylic acid units selected from the group consisting of carboxylic acid units and aliphatic hydroxycarboxylic acid units represented by the following formula (4), and aliphatic unsaturation represented by the following formula (5) One or more aliphatic units selected from the group consisting of a dicarboxylic acid unit, an aliphatic unsaturated dicarboxylic acid unit represented by the following formula (6), and an aliphatic unsaturated dicarboxylic acid unit represented by the following formula (7): at least look at containing the saturated dicarboxylic acid units,
The total amount of the units represented by the formula (3), the formula (4), the formula (5), the formula (6) and the formula (7) is the total amount of all units contained in the aliphatic polyester resin. The total of the units represented by the formula (3) and the formula (4) is 0.0010 mol% or more and 0.50 mol% or less with respect to the total amount of 100 mol%. (6) and molar ratio to the total of the unit represented by the formula (7) state, and are 1.0 to 7.0, with respect to 100 parts by weight of the aliphatic polyester resin, the organic peroxide Is mixed at a ratio of 0.0001 parts by weight or more and 0.06 parts by weight or less, and a method for producing a biodegradable laminated sheet .

(In the formula, R ¹ represents an aliphatic saturated hydrocarbon group having 0 to 40 carbon atoms.)

(In the formula, R ² represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms.)

(In the formula, R ³ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)

(In the formula, R ⁴ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)

(In the formula, R ⁵ represents a C 2-20 aliphatic hydrocarbon group having one or more double bonds.)

(Formula (6) and Formula (7) are both geometrical isomers relating to a double bond, wherein Formula (6) represents a trans form, and Formula (7) represents a cis form. And represents an integer of 0 to 17. R ⁸ represents hydrogen or an aliphatic hydrocarbon group having 1 to 17 carbon atoms. The unit represented by the formula (5) is an aliphatic unsaturated dicarboxylic acid unit represented by the following formula (8) and / or the following formula (9):
The molar ratio of the unit represented by the formula (8) contained in the aliphatic polyester resin is 8.5 or less with respect to the unit represented by the formula (9). Item 2. A method for producing a biodegradable laminated sheet according to Item 1.

(Formula (8) and Formula (9) are both geometrical isomers relating to a double bond, wherein Formula (8) represents a trans form, and Formula (9) represents a cis form. And represents an integer of 0 to 18. R ⁶ and R ⁷ each independently represents hydrogen or an aliphatic hydrocarbon group having 1 to 18 carbon atoms. The organic peroxide is at least one compound selected from the group consisting of ketone peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, and hydroperoxide. The manufacturing method of the biodegradable laminated sheet of Claim 1 or 2 characterized by the above-mentioned. The biodegradable laminated sheet according to any one of claims 1 to 3, wherein the base material contains at least one selected from paper, cellophane, non-woven fabric, polylactic acid film, and polyglycolic acid film. Manufacturing method .